JP5358870B2 - Aqueous resin dispersion and method for producing the same, paint, laminate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a resin excellent in stability and useful as a coating for an olefin-based polymer, and a coating material. <P>SOLUTION: This aqueous resin dispersion is provided by dispersing each of particles consisting of a polymer (C) containing a propylene-based polymer (A) and particles consisting of at least &ge;1 selected from a group consisting of an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin and a vinyl ester-based resin in water and satisfying a specific relationship. The coating material is also provided. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to an aqueous dispersion containing a propylene-based polymer resin and a coating material containing the same.

  Polyolefins such as propylene polymers and propylene-α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, etc., so they are used in a wide range of fields. . However, such polyolefins generally have a low polarity because they do not have a polar group in the molecule, and it is difficult to paint and bond, and improvements have been desired. For this reason, various methods have been tried, such as chemically treating the surface of a molded product of polyolefin with a chemical or the like, and oxidizing the surface of the molded product by a method such as corona discharge treatment, plasma treatment, or flame treatment. Yes. However, in these methods, not only a special apparatus is required but also the effect of improving paintability and adhesiveness is not always sufficient.

  Therefore, as a device for imparting good paintability and adhesiveness to polyolefins such as propylene polymers by a relatively simple method, so-called chlorinated polypropylene, acid-modified propylene-α-olefin copolymers, and further acid-modified chlorine Polypropylene has been developed. Such a modified polyolefin is applied as a surface treatment agent, an adhesive, a paint or the like to the surface of the polyolefin molded body. The modified polyolefin is usually applied in the form of a solution of an organic solvent or a dispersion in water. In general, an aqueous dispersion is preferably used from the viewpoint of health and safety and reduction of environmental pollution.

  For example, an aqueous resin in which acid-modified chlorinated polypropylene is made aqueous using a surfactant and a basic substance (Patent Document 1) or an aqueous resin in which acid-modified polyolefin is made aqueous using a surfactant and a basic substance (Patent Documents 2 and 3). However, in these methods, it is necessary to add a large amount of a surfactant in order to reduce the dispersed particle size. As a result, there is a problem that paints using such an aqueous dispersion have poor water resistance and chemical resistance. there were. Further, the surfactant may bleed out to the painted surface after coating, resulting in poor appearance, and further improvement has been desired.

  In addition, when these modified polyolefins are used as water-based paints or inks, binder resins such as acrylic resins, polyurethane resins, polyester resins, vinyl acetate resins, and epoxy resins are usually used to satisfy performance other than adhesion. If necessary, pigments such as titanium oxide and carbon black are blended. However, since these components generally do not have high adhesion to the propylene polymer substrate, even if the propylene polymer resin alone has sufficient substrate adhesion, the substrate adhesion is greatly improved after mixing. However, there is a problem of lowering.

For this reason, there is an example of a water-based paint (Patent Document 4) in which an ethylene polymer resin having a small particle diameter is blended with a binder resin such as an acrylic resin. Further, it is difficult to emulsify, and there has been a strong desire to solve the above problems in water-based paints containing a propylene polymer.
JP-A-3-182534 Japanese Patent Laid-Open No. 6-256592 JP2004002842 JP 2004-083787 A

  The present invention provides an aqueous dispersion of a resin and a paint which are excellent in stability and are useful as a paint for an olefin polymer.

As a result of intensive studies to achieve the above object, the present inventors have found that a polymer containing a propylene polymer and a specific resin are each dispersed in water, and an aqueous resin dispersion in which they have a specific relationship is a polyolefin. It has been found that it has excellent adhesion to the substrate, moisture resistance and oil resistance, and has led to the present invention.
That is, the present invention provides at least one or more particles selected from the group consisting of particles composed of a polymer (C) containing a propylene-based polymer (A), and acrylic resin, polyester resin, polyurethane resin, epoxy resin, and vinyl ester resin. Particles made of resin (D) are each dispersed in water, the polymer (C) is represented by propylene polymer (A) and the carboxylic acid derivative group is represented by -C (= O) O-. A polyether resin having an amino group as a hydrophilic polymer (B) is graft- bonded to the carboxylic acid derivative group in a ratio of 0.01 to 5 mmol / g in terms of a group , and The present invention relates to an aqueous resin dispersion satisfying the following (1) to (4).
(1) The mass ratio of the propylene polymer (A) to the resin (D) is 90:10 to 10:90. (2) The total amount of the polymer (C) and the resin (D) and the mass of water. The ratio is 5:95 to 60:40 (3) The surfactant content is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer (C) and the resin (D) (4) polymer ( The volume average particle diameter of the particles made of C) is 0.5 μm or less, and is 0.9 times or less of the volume average particle diameter of the particles made of the resin (D). Is a water-based resin which is a polymer obtained by bonding a hydrophilic polymer (B) to a propylene polymer (A) at a ratio of (A) :( B) = 100: 5 to 100: 500 (mass ratio). Concerning the dispersion.

The present invention also relates to an aqueous resin dispersion in which the propylene-based polymer (A) is a stereoblock polypropylene polymer having an isotactic block and an atactic block.
In the present invention, the propylene-based polymer (A) is a stereoblock polypropylene polymer containing an isotactic block and an atactic block, and a propylene unit chain part comprising a head-to-tail bond in ¹³ C-NMR. A peak appearing from 19.8 ppm to 22.1 ppm when the peak derived from the carbon atom of the methyl group was observed and the chemical shift of the peak top attributed to the pentad represented by mmmm was 21.8 ppm The ratio of the peak area S ₁ having a peak top of 21.8 ppm to the total area S (S ₁ / S) of 20% to 70% and the peak having 21.5 to 21.7 ppm as the peak top area to aqueous resin dispersion is a _{4 + 2S 1 / S 2>} 5 when the _{S 2} of (mmmr).

In the present invention, the propylene polymer (A) is a propylene-1-butene copolymer, the propylene content is 50 mol% or more and 95 mol% or less, and the molecular weight distribution Mw of the copolymer (A). The present invention relates to an aqueous resin dispersion having a / Mn of 3.0 or less and a melting point Tm of 120 ° C. or less.
The present invention also relates to an aqueous resin dispersion in which the propylene polymer (A) is produced using a metallocene catalyst.

Further, the present invention further includes a pigment (E), and an aqueous resin dispersion in which the mass ratio of the total amount of the polymer (C) and the resin (D) to the pigment (E) is 100: 10 to 100: 400 About the body.
Further, in the present invention, the carboxylic acid derivative group is bonded to the propylene polymer (A) at a rate of 0.01 to 5 mmol / g in terms of a group represented by -C (= O) O-, A polymer obtained by graft- bonding a polyether resin having an amino group as a hydrophilic polymer (B) to an acid derivative group at a ratio of (A) :( B) = 100: 5 to 100: 500 (mass ratio) A dispersion obtained by dispersing (C) in water and at least one resin (D) selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl ester resin are dispersed in water. The resulting dispersion is mixed, the mass ratio of the propylene polymer (A) and the resin (D) is 90:10 to 10:90, the total amount of the polymer (C) and the resin (D), and water. And a mass ratio of 5:95 to 60:40 Method for producing an aqueous resin dispersion to obtain a certain aqueous resin dispersion related.

Furthermore, the present invention relates to a paint comprising the aqueous resin dispersion.
Furthermore, this invention relates to the manufacturing method of the laminated body which apply | coats the said aqueous resin dispersion or the said coating material to a thermoplastic resin molding (F), and forms a resin layer by heating.
The present invention also includes a polymer (C) containing a propylene polymer (A), an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl ester resin on a thermoplastic resin molded body (F). At least one resin (D) selected from the group consisting of (A) :( D) in a mass ratio of 90:10 to 10:90, and the polymer (C) is a propylene polymer (A) The carboxylic acid derivative group is bonded to the group represented by —C (═O) O— at a rate of 0.01 to 5 mmol / g, and the carboxylic acid derivative group is bonded to the carboxylic acid derivative group as a hydrophilic polymer (B). are those polyether resin having an amino group is formed by grafted, and a layer not more than 10 parts by weight per 100 parts by weight of the surfactant content polymer (C) and the resin (D) It relates to a laminate having the same.

  Moreover, this invention relates to the laminated body in which the resin layer is formed by apply | coating the said aqueous resin dispersion or the said coating material to a thermoplastic resin molding (F), and heating.

  Since the polymer (C) of the present invention is excellent in water dispersibility, an aqueous resin dispersion excellent in the stability of finely dispersed particles can be obtained by adding a small amount of surfactant or without adding a surfactant. can get. Therefore, the composite aqueous resin dispersion containing the polymer (C) and the resin (D) has an advantage that bleeding out due to the surfactant, which has been a problem in the past, can be suppressed, and thus a coated product having an excellent appearance can be obtained. Therefore, aqueous dispersions can be used for applications that have conventionally been applied as organic solvent solutions, which is also preferable in terms of safety and hygiene. Further, since it is not an organic solvent solution, VOC (volatile organic chemical substance) emission can be reduced, which is preferable from the environmental viewpoint. In addition, an aqueous dispersion having excellent properties can be obtained without substantially containing chlorine. When chlorine is not included, there are no problems such as dioxin and toxicity, which is very preferable in terms of environment.

  In addition, since the particle size of the polymer (C) particles is as small as 0.9 times or less than the particle size of the resin (D) particles, voids between the resin (D) particles are formed in the polymer (C ) There is an advantage that the particles are filled and the void volume is reduced, the adhesion to the substrate is high, and the water resistance and solvent resistance are improved. Furthermore, in the coating film, a sea-island structure in which the propylene-based polymer having high adhesion to the propylene-based polymer substrate is “the sea” and other binder resins that give other functions to the coating film are “islands”. Since it is formed, there is an advantage that the adhesion to the substrate is higher and the water resistance and solvent resistance are improved.

According to the method for producing a resin dispersion of the present invention, an excellent aqueous resin dispersion having a fine dispersed particle diameter, a narrow particle size distribution, and stably dispersed resin particles can be easily obtained.
Furthermore, the coating film obtained by applying the paint containing the resin dispersion of the present invention is excellent in water resistance, moisture resistance, oil resistance (GH resistance) and chemical resistance. For this reason, it is also suitable for a coating method such as a solvent-based lacquer type paint which is finished by only one coating.

  The obtained coating film shows good adhesion to polyolefin materials, especially propylene polymer materials, or plastic materials containing propylene polymer materials, etc., such as untreated polypropylene, which is usually difficult to paint and bond It can also be formed on a hardly adhesive substrate. Moreover, since it is a composite aqueous resin dispersion containing the resin (D) together with the polymer (C), the physical property value derived from the resin (D) is improved, specifically, the strength, water resistance, weather resistance, resistance of the coating film. Rubability, solvent resistance, etc. can be improved.

Therefore, the aqueous resin dispersion of the present invention is extremely useful as a surface treatment agent, a coating agent, a paint, and the like for a crystalline olefin polymer.
Further, the laminate of the present invention is excellent in coating film adhesion and can be applied to a wide range of industrial products.
In the present invention, it is only necessary to have one or more of the above-described effects even if not all the effects are manifested.

The aqueous resin dispersion of the present invention is selected from the group consisting of particles made of a polymer (C) containing a propylene polymer (A), and acrylic resin, polyester resin, polyurethane resin, epoxy resin, and vinyl ester resin. Particles composed of at least one resin (D) are each dispersed in water and satisfy the following (1) to (4).
(1) The mass ratio of the propylene polymer (A) to the resin (D) is 90:10 to 10:90. (2) The total amount of the polymer (C) and the resin (D) and the mass of water. The ratio is 5:95 to 60:40 (3) The surfactant content is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer (C) and the resin (D) (4) polymer ( The volume average particle diameter of the particles made of C) is 0.5 μm or less, and is 0.9 times or less the volume average particle diameter of the particles made of resin (D). It is a concept that includes a state of being extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved.

  By using the resin (D) in combination with the polymer (C), the polymer (C) has a high adhesion to a polyolefin substrate and a high adhesion to a resin other than a polyolefin that cannot be achieved by the polymer (C) alone. Can also be obtained. Moreover, there exists an advantage which can improve physical properties, such as the intensity | strength of a coating film, water resistance, a weather resistance, abrasion resistance, and solvent resistance. Furthermore, there are effects such as improvement of the appearance of coating (glossing or matting) and reduction of tackiness.

  In the present invention, in order to effectively exhibit the properties of the polymer (C) and the resin (D), the particles made of the polymer (C) and the particles made of the resin (D) are separately dispersed in water. Exists. Such an aqueous resin dispersion is obtained by, for example, mixing a dispersion obtained by emulsifying and dispersing the polymer (C) in water and a dispersion obtained by emulsifying and dispersing the resin (D) in water. can get.

  The mass ratio of the propylene polymer (A) and the resin (D) is 90:10 to 10:90. That is, the total amount of the propylene polymer component and the other resin is 100 parts by mass, and the amount of the propylene polymer (A) is 10 parts by mass or more and 90 parts by mass or less. When the amount of the propylene polymer (A) is less than 10 parts by mass, the adhesion to the propylene polymer substrate is insufficient. Preferably it is 15 mass parts or more, More preferably, it is 20 mass parts or more. When the amount of the propylene-based polymer (A) is larger than 90 parts by mass, the physical properties of the coating film obtained from such a composite aqueous resin dispersion, specifically, the strength, water resistance, weather resistance, abrasion resistance of the coating film. And solvent resistance will be insufficient. Preferably it is 80 mass parts or less, More preferably, it is 70 mass parts or less.

  The mass ratio of the total amount of the polymer (C) and the resin (D) to water is 5:95 to 60:40. That is, the total amount of the polymer (C) and the resin (D) is 5 parts by mass or more and 60 parts by mass or less with the total amount of the polymer (C), the resin (D) and water being 100 parts by mass. If it is less than 5 mass parts, workability | operativity, such as application | coating and heat curing, is bad and is not practical. Preferably it is 10 mass parts or more, More preferably, it is 15 mass parts or more. When it is larger than 60 parts by mass, the viscosity of the aqueous resin dispersion becomes too high, the applicability is deteriorated, and it is difficult to form a uniform coating film. Preferably it is 55 mass parts or less, More preferably, it is 50 mass parts or less.

Surfactant content shall be 10 mass parts or less with respect to 100 mass parts of resin components (total amount of a polymer (C) and resin (D)). Further, the volume average particle diameter of the particles made of the polymer (C) is 0.5 μm or less and 0.9 times or less the volume average particle diameter of the particles made of the resin (D).
The volume average particle diameter is also referred to as median diameter, 50% particle diameter, 50% average particle diameter, and the like.
Since the propylene-based copolymer (A) according to the present invention is very excellent in dispersibility in water, the dispersion particle size is small and the particle size distribution is small by using a very small amount without using any surfactant. A narrow aqueous resin dispersion in which particles are stably dispersed can be obtained. Thereby, when this resin dispersion is used as a coating material, a bleed-out can be suppressed and a coated product excellent in appearance can be obtained, and the water resistance and oil resistance (GH resistance) of coating can be improved.

  The 50% particle diameter of the polymer (C) particles is preferably 0.3 μm or less, more preferably 0.2 μm or less, and most preferably 0.1 μm or less. Similarly, when the 90% particle diameter is determined, the 90% particle diameter can be more preferably 1 μm or less, and particularly preferably 0.5 μm or less. By reducing the dispersed particle size, the dispersion stability is improved, aggregation is unlikely to occur, and the dispersion can be more stably dispersed. Further, a reduction in the ratio of the 90% particle diameter to the 50% particle diameter means that the particle size distribution becomes narrow, and as a result, the dispersion stability is improved. In the present invention, the term “dispersion” is a concept including a state in which dispersed particles are extremely small and dispersed in a single molecule, and a state that can be said to be substantially dissolved. Accordingly, there is no particular limitation on the lower limit value of the dispersed particle size.

  The polymer (C) particles have a particle size of 0.9 times or less that of the resin (D) particles, so that the voids between the resin (D) particles are formed when the coating film is formed. (C) The particles are filled and the void volume is reduced, the adhesion to the substrate is high, and the water resistance and solvent resistance are improved. Furthermore, in the coating film, a sea-island structure in which the propylene-based polymer having high adhesion to the propylene-based polymer substrate is “the sea” and other binder resins that give other functions to the coating film are “islands”. Since it forms, the adhesiveness to a base material is still higher, and water resistance and solvent resistance improve. The particle size of the polymer (C) particles is preferably 0.8 times or less, more preferably 0.6 times or less than the particle size of the resin (D) particles.

The polymer (C) is preferably formed by bonding the hydrophilic polymer (B) or the acidic group to the propylene polymer (A). Since such a polymer (C) is very excellent in dispersibility in water, the dispersion particle size is small and the particle size distribution is narrow and the particles are stable by using a very small amount without using any surfactant. A dispersed aqueous resin dispersion is obtained.
More preferably, the polymer (C) contains the hydrophilic polymer (B) in the ratio of (A) :( B) = 100: 5 to 100: 500 (weight ratio) to the propylene-based polymer (A). Combined. The ratio of the propylene polymer (A) to the hydrophilic polymer (B) is (A) :( B) = 100: 5 to 100: 500 parts by weight. If the ratio of the hydrophilic polymer (B) is smaller than this range, the polymer (C) will not be dispersed well in water, and the dispersed particle size will be very large, or will be aggregated or separated. On the contrary, when the ratio of the hydrophilic polymer (B) is larger than this range, the adhesion with the propylene-based polymer substrate is deteriorated.

  As a method for producing a polymer (C) by combining a propylene polymer (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the propylene polymer (A) to produce propylene. Method for forming hydrophilic polymer (B) bonded to polymer (A) (R1), or method for bonding previously polymerized hydrophilic polymer (B) to propylene polymer (A) (R2) And may be appropriately selected according to the type and combination of polypropylene and hydrophilic polymer, the characteristics of the target polymer (C), and the like. Moreover, as a propylene polymer (A), the polypropylene polymer (A1) which does not have a reactive group, or the polypropylene polymer (A2) which has a reactive group can be used.

This will be described in more detail below.
[1] Propylene polymer (A)
The propylene polymer (A) of the present invention is a polymer having a propylene content of 50 mol% or more. The propylene content is preferably 60 mol% or more, more preferably 70 mol% or more. Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate.
As the propylene polymer (A) of the present invention, a propylene polymer (A1) having no reactive group or a propylene polymer (A2) having a reactive group can be used.

[1-1] Propylene polymer having no reactive group (A1)
As the propylene polymer (A1), various known propylene polymers and modified propylene polymers can be used, and are not particularly limited. For example, a propylene homopolymer, an ethylene and propylene copolymer, Copolymers of propylene and other comonomers such as butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and α-olefin comonomers having 2 or more carbon atoms such as norbornene, Alternatively, two or more types of copolymers of these comonomers can be used. The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 6 carbon atoms. Also, a copolymer of an α-olefin monomer and a comonomer such as vinyl acetate, acrylic acid ester, and methacrylic acid ester, a copolymer of a comonomer such as an aromatic vinyl monomer, a hydrogenated product thereof, a conjugated diene block copolymer, or The hydrogenated product can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. Furthermore, a chlorinated propylene polymer obtained by chlorinating these propylene polymers can also be used. The chlorination degree of the chlorinated propylene polymer is usually 5% by mass or more, preferably 10% by mass or more, and the chlorination degree is usually 50% by mass or less, preferably 30% by mass or less.

  Specific examples of the propylene polymer (A1) include, for example, polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer, propylene-hexene copolymer, and chlorinated polypropylene. Chlorinated ethylene-propylene copolymer, chlorinated propylene-butene copolymer, and the like. Preferably, it is a propylene homopolymer or a copolymer of propylene and another α-olefin, and these may be chlorinated. More preferably, propylene homopolymer, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, or chlorinated propylene- It is a butene copolymer.

These may be used individually by 1 type and may be used in combination of 2 or more type.
The propylene-based polymer (A1) in the present invention preferably has a weight average molecular weight Mw of 1,000 to 500,000 as measured by GPC (Gel Permeation Chromatography) and converted with a calibration curve of each propylene polymer. . A more preferable value of the lower limit value is 10,000, more preferably 30,000, and particularly preferably 50,000. A more preferable value of the upper limit value is 300,000, more preferably 250,000, and particularly preferably 200,000. As Mw is higher than the lower limit, the degree of stickiness tends to decrease and the adhesion to the substrate tends to increase, and as the Mw is lower than the upper limit, the viscosity tends to decrease and the resin dispersion tends to be easily prepared. The GPC measurement is performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent.

  As one of the most preferable forms of the propylene homopolymer or copolymer, those having an isotactic structure in whole or in part as stereoregularity are preferable. For example, not only normal isotactic polypropylene but also isotactic block polypropylene, stereo block polypropylene, etc. as described in JP-A-2003-231714 and US Pat. No. 4,522,982 should be used. Can do.

Preferably, the propylene polymer (A1) is a stereoblock polypropylene homopolymer or copolymer having an isotactic block and an atactic block. Most preferred is a stereoblock polypropylene polymer having an isotactic block and an atactic block.
More preferably, in ¹³ C-NMR, a peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond is observed, and the peak of the peak attributed to the pentad represented by mmmm is observed. When the chemical shift is 21.8 ppm, the ratio (S ₁ / S) of the peak area S ₁ having 21.8 ppm as the peak top to the total peak area S appearing from 19.8 ppm to 22.1 ppm is 20 % To 70%. A preferable value of the lower limit is 30%, more preferably 35%, and more preferably 40%. A preferable value of the upper limit is 65%, more preferably 60%, and more preferably 55%. There is a tendency that the degree of stickiness becomes smaller as the value is lower than the lower limit, and the degree of crystallinity becomes lower and the preparation of the resin dispersion tends to become easier as the value is lower than the upper limit.

More preferably, 4 + 2S ₁ / S ₂ > 5, where S ₂ is an area of a peak (mmmmr) having a peak top of 21.5 to 21.7 ppm. As a method for measuring the pentad ratio, the method described in JP-A-2003-231714 can be used.
Alternatively, the propylene polymer (A1) is a propylene-1-butene copolymer, the propylene content is 50 mol% to 95 mol%, and the molecular weight distribution Mw / Mn of the copolymer (A1) is 3. Those that are 0 or less are also preferred. Since such a copolymer has a lower melting point than that of a propylene homopolymer, a resin dispersion using the copolymer has an advantage that the baking temperature after coating can be lowered.

  Usually, the higher the propylene content, the higher the adhesion to the polypropylene substrate. Preferably it is 60 mol% or more, More preferably, it is 70 mol% or more. However, the propylene content is 95 mol% or less. Usually, when the propylene content is lowered, the melting point of the copolymer can be lowered, and for example, there is an advantage that the baking temperature after coating can be lowered. Preferably it is 90 mol% or less, More preferably, it is 85 mol% or less.

The 1-butene content is preferably 5 mol% to 50 mol%. More preferably, it is 10 mol% or more, More preferably, it is 15 mol% or more. More preferably, it is 40 mol% or less, More preferably, it is 30 mol% or less.
The copolymer (A1) may contain a small amount of a structural unit derived from an α-olefin other than propylene and 1-butene. For example, 10 mol% or less of ethylene may be included. More preferably, it is 5 mol% or less.

The copolymer (A1) may be a random copolymer or a block copolymer, but is preferably a random copolymer. The melting point of the copolymer can be lowered more effectively. The copolymer (A1) may be linear or branched.
Preferably, the copolymer (A1) has a molecular weight distribution Mw / Mn represented by a ratio of the weight average molecular weight Mw to the number average molecular weight Mn of 3.0 or less. This means that the molecular weight distribution is narrow and the molecular weight of the copolymer is uniform. By using such a copolymer (A1), it is easy to control the particle size during dispersion in water. Thus, there is an advantage that a dispersed resin particle having a small dispersed particle size, a narrow particle size distribution, and a stable dispersion can be obtained. More preferably, it is 2.5 or less. However, it is usually 1.0 or more. The molecular weight distribution Mw / Mn is determined by gel permeation chromatography (GPC).

  More preferably, the copolymer (A1) has a melting point Tm of 120 ° C. or less. More preferably, it is 100 degrees C or less, More preferably, it is 90 degrees C or less. The melting point Tm lower than 120 ° C. is preferable because the crystallinity is low and the solubility in a solvent is improved, and the emulsification / dispersion work is easily performed at a low temperature. In addition, when this resin dispersion is used, for example, as a paint or an adhesive, it is advantageous in that it melts at a low baking temperature. However, the melting point Tm of the copolymer (A1) is usually 35 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, and most preferably 70 ° C. or higher. . It is free in terms of high heat resistance, high hardness and non-stickiness. The melting point Tm can be measured by a differential scanning calorimeter (DSC).

Commercially available products available as the copolymer (A1) include Tafmer XM-7070 and XM-7080 manufactured by Mitsui Chemicals.
About the manufacturing method of the propylene-type polymer (A1) of this invention, if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, What kind of manufacturing method may be sufficient. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like may be mentioned, and each may be living polymerization.

In the case of coordination polymerization, for example, a polymerization method using a Ziegler-Natta catalyst or a polymerization method using a single site catalyst or a Kaminsky catalyst can be used. A preferable production method includes a production method using a single site catalyst. This is because the molecular weight distribution and stereoregularity distribution of single-site catalysts are generally sharp due to the ligand design. Moreover, as a single site catalyst, a metallocene catalyst and a Brookhart type catalyst can be used, for example. C ₁ symmetric type metallocene catalyst, C ₂ symmetric, C _2V symmetric, C _S symmetric like, it may be selected preferred catalyst in accordance with the stereoregularity of polymerized propylene polymer. Preferably, a C ₁ symmetric type or C ₂ symmetric type metallocene catalyst can be used.

The polymerization may be any polymerization form such as solution polymerization, slurry polymerization, bulk polymerization, and gas phase polymerization. In the case of solution polymerization or slurry polymerization, examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic carbonization such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrogen, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Examples include alcohols such as ethanol, n-propanol, isopropanol, and n-butanol; ethers such as dibutyl ether and tetrahydrofuran; and polar solvents such as dimethylformamide and dimethyl sulfoxide. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and toluene, xylene, hexane, heptane, cyclopentane, and cyclohexane are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.
The propylene polymer (A1) may be linear or branched.

[1-2] Propylene polymer having a reactive group (A2)
Examples of the propylene-based polymer (A2) having a reactive group include a copolymer (A2a) obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group at the time of polymerization, or A polymer (A2b) obtained by graft polymerization of a radically polymerizable unsaturated compound having a reactive group to a propylene-based polymer can be used.

  The copolymer (A2a) is obtained by copolymerizing an unsaturated compound having no reactive group and an unsaturated compound having a reactive group, and the unsaturated compound having a reactive group is inserted into the main chain. Copolymer. For example, it can be obtained by copolymerizing an α-olefin such as ethylene, propylene or butene and an α, β-unsaturated carboxylic acid or anhydride such as acrylic acid or maleic anhydride. Specifically as a copolymer (A2a), a propylene-acrylic acid copolymer, a propylene-acrylic acid ester-maleic anhydride copolymer etc. can be used, for example. These may be used individually by 1 type and may be used in combination of 2 or more type. As the manufacturing method, the method described in (A1) can be similarly used.

  The polymer (A2b) is obtained by graft-polymerizing a prepolymerized propylene polymer with a radically polymerizable unsaturated compound having a reactive group, and the unsaturated compound having a reactive group is grafted to the main chain. Yes. For example, (meth) acrylic acid, fumaric acid, maleic acid or anhydride thereof, itaconic acid or anhydride thereof, crotonic acid, (meth) acrylic acid 2-propylene polymer such as polypropylene and propylene-butene copolymer Graft hydroxyethyl, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, (dimethylamino) ethyl (meth) acrylate, glycidyl (meth) acrylate, (2-isocyanato) ethyl (meth) acrylate, etc. Polymer. These may be used individually by 1 type and may be used in combination of 2 or more type. In addition, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid, and others are based on this.

As the propylene polymer of this reaction, the above-mentioned propylene polymer (A1) having no reactive group can be used.
Specific examples of the polymer (A2b) include, for example, maleic anhydride-modified polypropylene and its chlorinated product, maleic anhydride-modified ethylene-propylene copolymer and its chlorinated product, maleic anhydride-modified propylene-butene copolymer, and acrylic acid. Examples thereof include modified polypropylene and chlorinated products thereof, acrylic acid-modified ethylene-propylene copolymers and chlorinated products thereof, and acrylic acid-modified propylene-butene copolymers. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The radical polymerization initiator used for the graft polymerization can be appropriately selected from ordinary radical initiators, and examples thereof include organic peroxides and azonitriles. Examples of organic peroxides include peroxyketals such as di (t-butylperoxy) cyclohexane, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as di (t-butyl) peroxide, and benzoyl peroxide. Diacyl peroxides such as oxides and peroxyesters such as t-butylperoxyisopropyl monocarbonate can be used. Examples of the azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Of these, benzoyl peroxide and t-butylperoxyisopropyl monocarbonate are particularly preferred. These may be used individually by 1 type and may be used in combination of 2 or more type.

The use ratio of the radical polymerization initiator and the graft copolymer unit is usually in the range of radical polymerization initiator: graft copolymer unit = 1: 100 to 2: 1 (molar ratio). Preferably it is the range of 1: 20-1: 1.
The reaction temperature is usually 50 ° C. or higher, preferably in the range of 80 to 200 ° C. The reaction time is usually about 2 to 20 hours.

  About the manufacturing method of a polymer (A2b), if the polymer which satisfy | fills the requirements of this invention can be manufactured, it will not specifically limit, Any manufacturing method may be sufficient. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

  The content of the reactive group in the propylene polymer (A2) having a reactive group is preferably in the range of 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g per 1 g of the propylene polymer. A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. A more preferred upper limit is 1 mmol / g, and even more preferably 0.8 mmol / g. The higher the lower limit value, the more the hydrophilic polymer (B) is bound and the higher the hydrophilicity of the polymer (C). Therefore, the dispersed particle size tends to decrease. The lower the upper limit value, the lower the crystallinity of the base material. There exists a tendency for the adhesiveness with respect to a propylene polymer to increase.

The propylene polymer (A2) may be linear or branched.
In the present invention, both the propylene polymer (A1) having no reactive group and the propylene polymer (A2) having a reactive group are combined with the hydrophilic polymer (B) or the intended polymer. Although it can use suitably according to the characteristic etc. of (C), Preferably it is a propylene polymer (A2) which has a reactive group. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B) and various reactions that can be used for binding.

  Examples of reactive groups include carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups, hydroxyl groups, amino groups, epoxy groups, and isocyanate groups. More preferably, the propylene polymer (A) has at least one selected from the group consisting of carboxylic acid derivative groups, that is, carboxylic acid groups, dicarboxylic anhydride groups, and dicarboxylic anhydride monoester groups. These carboxylic acid groups and the like are not only highly reactive and easy to bond to hydrophilic polymers, but also many unsaturated compounds having these groups can be easily copolymerized or grafted to a propylene polymer.

In the case of a carboxylic acid derivative group, the content of the reactive group is an amount converted to a group represented by -C (= O) O-. That is, since the dicarboxylic acid anhydride group can be regarded as including two carboxylic acid groups in the group, 1 mol of the dicarboxylic acid anhydride group is counted as 2 mol of the reactive group.
Moreover, although both a polymer (A2a) and a polymer (A2b) can be used, a polymer (A2b) is preferable normally. There are advantages such as easy control of the binding amount of the hydrophilic polymer (B).

[2] Polymer (C) in which acidic group is bonded to propylene polymer (A)
What propylene-type polymer (A) couple | bonded with the acidic group can also be used as it is as polymer (C).
The acidic group in the present invention refers to an electron pair accepting group, and is not particularly limited. For example, a carboxylic acid group (—COOH), a sulfo group (—SO ₃ H), a sulfino group (—SO ₂ H), a phosphono group _(-PO 2 H), and the like. The carboxylic acid group may be in a dicarboxylic anhydride group (—CO—O—OC—) before being dispersed in water. Among these, at least one selected from the group consisting of a carboxylic acid derivative group, that is, a carboxylic acid group, a dicarboxylic anhydride group, and a dicarboxylic anhydride monoester group is preferable. Examples of the carboxylic acid derivative group include (meth) acrylic acid group, fumaric acid group, maleic acid group or anhydride group thereof, itaconic acid group or anhydride group thereof, and crotonic acid group.

  The binding amount of the acidic group is preferably in the range of 0.4 to 5 mmol, that is, 0.4 to 5 mmol / g, per 1 g of the propylene polymer (A). A more preferred lower limit is 0.6 mmol / g, and a more preferred lower limit is 0.8 mmol / g. A more preferred upper limit is 3 mmol / g, and a more preferred upper limit is 1.6 mmol / g. The higher the lower limit value, the higher the polarity of the polymer and the higher the hydrophilicity, so the dispersed particle size tends to decrease. The lower the upper limit value, the higher the adhesion to the crystalline polyolefin as the substrate. In the case of a carboxylic acid derivative group, the content of the acidic group is an amount converted to a group represented by -C (= O) O-.

[3] Hydrophilic polymer (B)
In the present invention, the hydrophilic polymer means a polymer having an insoluble content of 1% by mass or less when dissolved in water at 25 ° C. at a concentration of 10% by mass. The hydrophilic polymer (B) is not particularly limited as long as the effects of the present invention are not significantly impaired, and any of synthetic polymers, semi-synthetic polymers, and natural polymers can be used. It may have a reactive group.
Although it does not specifically limit as a synthetic polymer, For example, a poly (meth) acryl resin, polyether resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin etc. can be used. Examples of natural polymers include, but are not limited to, starch such as corn starch wheat starch, candy starch, potato starch, tapioca starch, and rice starch, seaweed such as fungi, agar and sodium alginate, gum arabic, tragacanth gum, and konjac. Animal materials such as quality materials, glue, casein and gelatin, fermented mucilages such as pullulan and dextrin, and the like can be used. The semi-synthetic polymer is not particularly limited, and for example, starch such as carboxyl starch, cationic starch, and dextrin, viscose, cellulose such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, and hydroxyethyl cellulose can be used.

  Among these, a synthetic polymer that can easily control the degree of hydrophilicity and has stable characteristics is preferable. More preferred are acrylic resins such as poly (meth) acrylic resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, and polyether resins. These may be used individually by 1 type and may be used in combination of 2 or more type. Highly hydrophilic polyether resins are most preferred.

  The acrylic resin used in the present invention is usually obtained by polymerizing an unsaturated carboxylic acid or its ester or anhydride by radical polymerization, anionic polymerization, or cationic polymerization. The bonding method with the propylene-based polymer (A) is not limited. For example, a method of radical graft polymerization directly on the propylene-based polymer, a reactive group such as a hydroxyl group, an amino group, a glycidyl group, or an (anhydrous) carboxylic acid group. And a method of reacting an acrylic resin having a reactive group with a propylene-based polymer having a reactive group.

Preferably, the unsaturated carboxylic acid or its ester or anhydride showing hydrophilicity is (meth) acrylic acid, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate dimethylaminoethyl quaternary (meth) acrylate And (meth) acrylamide.
The polyvinyl alcohol resin used in the present invention is usually obtained by polymerizing vinyl acetate to obtain polyvinyl acetate and then saponifying. The saponification degree may be complete saponification or partial saponification.

The polyvinyl pyrrolidone resin used in the present invention is usually obtained by polymerizing vinyl pyrrolidone.
The polyether resin used in the present invention is usually obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. The bonding method with the propylene-based polymer (A) is not limited. For example, a polyether obtained by ring-opening polymerization of a cyclic alkylene oxide in a propylene-based polymer having a reactive group, ring-opening polymerization, or the like. Examples thereof include a method of reacting a hydrophilic polymer having a reactive group such as polyol or polyetheramine with a propylene-based polymer having a reactive group.

Polyetheramine is a compound having a primary or secondary amino group as a reactive group at one or both ends of a resin having a polyether skeleton. Polyether polyol is a compound having hydroxyl groups as reactive groups at both ends of a resin having a polyether skeleton.
Preferred examples of the polyalkylene oxide and polyalkyleneimine exhibiting hydrophilicity include polyethylene oxide, polypropylene oxide, and polyethyleneimine.

Or as a polyetheramine, you may use Huntsman's Jeffamine M series, D series, ED series, etc.
The hydrophilic polymer (B) used in the present invention preferably has at least one reactive group capable of reacting with the propylene polymer (A) prior to bonding with the propylene polymer (A). Examples of the reactive group include a carboxylic acid group, a dicarboxylic acid anhydride group, and a dicarboxylic acid anhydride monoester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and preferably have at least an amino group. Since the amino group is highly reactive with various reactive groups such as a carboxylic acid group, a carboxylic anhydride group, a glycidyl group, and an isocyanate group, it is easy to bond a propylene polymer and a hydrophilic polymer. The amino group may be primary, secondary, or tertiary, but more preferably is a primary amino group.

The number of reactive groups may be one or more, but more preferably it has only one reactive group. When there are two or more reactive groups, there is a possibility that a three-dimensional network structure will be formed upon bonding with the propylene polymer (A), resulting in gelation.
However, even if it has a plurality of reactive groups, it is sufficient if only one reactive group is more reactive than the others. For example, a hydrophilic polymer having a plurality of hydroxyl groups and one amino group having a higher reactivity is a preferred example. Here, the reactivity is the reactivity with the reactive group of the propylene polymer (A).

  The hydrophilic polymer (B) in the present invention must be a polymer in order to impart sufficient hydrophilicity to the polymer (C), and is a weight average molecular weight measured by GPC and converted by a polystyrene calibration curve. It is assumed that Mw is 200 or more. The lower limit is preferably 300, more preferably 500. However, the weight average molecular weight Mw is preferably 200,000 or less. A more preferable value of the upper limit value is 100,000, and more preferably 10,000. As the Mw is higher than the lower limit, the hydrophilicity of the polymer (C) is increased and the dispersed particle size tends to be smaller and stably dispersed. As the Mw is lower than the upper limit, the viscosity is low and the resin dispersion tends to be easily prepared. . The GPC measurement is performed by a conventionally known method using a commercially available apparatus using THF or the like as a solvent.

  The amount of the hydrophilic polymer (B) bonded to the propylene polymer (A) is preferably in the range of 0.01 to 5 mmol, ie 0.01 to 5 mmol / g, per 1 g of the propylene polymer. . A more preferred lower limit is 0.05 mmol / g, even more preferably 0.1 mmol / g, and particularly preferably 0.15 mmol / g. A more preferred upper limit is 1 mmol / g, and even more preferably 0.8 mmol / g. The higher the lower limit value, the higher the hydrophilicity of the polymer (C) and the smaller the dispersed particle size tends to be stably dispersed. The lower the upper limit value, the higher the adhesion to the crystalline propylene-based polymer as the substrate. It tends to increase.

  The propylene polymer (A) and the hydrophilic polymer (B) are a graft copolymer in which the hydrophilic polymer (B) is graft-bonded to the propylene polymer (A), and a propylene polymer (A). There may be a block copolymer of a propylene-based polymer (A) and a hydrophilic polymer (B) including a state in which a hydrophilic polymer (B) is bonded to one or both ends, but preferably a graft copolymer It is a copolymer. There is an advantage that the content of the hydrophilic polymer (B) can be easily controlled and the content of the hydrophilic polymer (B) can be easily increased as compared with the block copolymer.

  Conventionally, there has been a method in which a carboxylic acid group is graft-bonded to a propylene polymer chain, and the carboxylic acid group is neutralized with a base and dispersed in water. According to the method of graft-bonding to the polymer chain, water dispersion is possible even if the number of moles of the group directly graft-bonded to the propylene polymer chain is considerably smaller than that of the conventional method. Accordingly, there is an advantage that the properties of the propylene-based polymer are not impaired and the adhesion to the polyolefin substrate is enhanced.

The hydrophilic polymer (B) can be bonded to the propylene polymer (A) by various reaction forms. Although the form is not specifically limited, For example, it is a reaction using a radical graft reaction or a reactive group.
According to the radical graft reaction, a bond by a carbon-carbon covalent bond is formed.
The reaction using a reactive group has a reactive group in both the propylene polymer (A) and the hydrophilic polymer (B) and reacts them to bond, and it is a covalent bond or ion A bond is formed. Examples of this reaction include esterification reaction of carboxylic acid group and hydroxyl group, ring-opening reaction of carboxylic acid group and epoxy group, ring-opening reaction of primary or secondary amino group and epoxy group, carboxylic acid group and 1 Amidation reaction of primary or secondary amino group, quaternary ammonium reaction of carboxylic acid group and tertiary amino group, urethanization reaction of carboxylic acid group and isocyanate group, primary or secondary amino group and isocyanate group Urethane reaction etc. are mentioned. The reaction rate of each reaction may be arbitrarily selected from 1 to 100%, preferably 50 to 100%, more preferably 70 to 100%. When the carboxylic acid group is a dibasic acid or an anhydride thereof, one equivalent or two equivalents may be reacted with respect to one equivalent of the dibasic acid or anhydride.

[4] Polymer (C) obtained by bonding hydrophilic polymer (B) to propylene polymer (A)
As a method for producing a polymer (C) by combining a propylene polymer (A) and a hydrophilic polymer (B), a hydrophilic monomer is usually polymerized in the presence of the propylene polymer (A) to produce propylene. Method for forming hydrophilic polymer (B) bonded to polymer (A) (R1), or method for bonding previously polymerized hydrophilic polymer (B) to propylene polymer (A) (R2) There is. In any case, as the propylene polymer (A), a propylene polymer (A1) having no reactive group or a propylene polymer (A2) having a reactive group can be used together.

[4-1] Method for producing polymer (C) (R1)
In this method, the hydrophilic polymer (B) bonded to the propylene polymer (A) is obtained by polymerizing the hydrophilic monomer in the presence of the propylene polymer (A). As a method for polymerizing the hydrophilic monomer, for example, addition polymerization, condensation polymerization, ring-opening polymerization and the like can be used. At this time, a hydrophobic monomer may be copolymerized as long as a hydrophilic polymer can be formed after polymerization.

  Specifically, for example, there is a method in which a hydrophilic radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a hydrophilic polymer (B) and bonded to the propylene polymer (A). is there. In this case, as the propylene polymer (A), a propylene polymer (A2) having a reactive group can also be used, but a propylene polymer (A1) having no reactive group is usually used.

  The hydrophilic radically polymerizable unsaturated compound is not particularly limited. For example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, ( Examples include methacrylic acid dimethylaminoethyl quaternized compounds, vinyl pyrrolidone and the like. Examples of the copolymerizable hydrophobic monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate.

  Alternatively, a method in which a radical polymerizable unsaturated compound is polymerized in the presence of a radical polymerization initiator to form a polymer and bonded to the propylene polymer (A), and then modified to obtain a hydrophilic polymer (B) There is. Examples thereof include a method of polymerizing t-butyl (meth) acrylate and then hydrolyzing it under acidic conditions to modify it into poly (meth) acrylic acid, and a method of polymerizing vinyl acetate and then saponifying and modifying it into polyvinyl alcohol. Examples of the copolymerizable hydrophobic monomer include (meth) acrylic acid esters such as methyl (meth) acrylate and butyl (meth) acrylate, and vinyl acetate. In this case, as the propylene polymer (A), a propylene polymer (A2) having a reactive group can also be used, but a propylene polymer (A1) having no reactive group is usually used.

Alternatively, a hydrophilic polymer is obtained by polymerizing a hydrophilic radical-polymerizable unsaturated compound, a hydrophilic ring-opening polymerization monomer, or the like using the propylene-based polymer (A2) having a reactive group and using the reactive group as a starting terminal. There is a method of obtaining (B).
As the hydrophilic radical-polymerizable unsaturated compound, those described above can be used similarly. Examples of the hydrophilic ring-opening polymerization monomer include ethylene oxide, propylene oxide, and ethyleneimine. Examples of the copolymerizable hydrophobic monomer include trimethylene oxide, tetrahydrofuran, β-propiolactone, γ-butyrolactone, and ε-caprolactone.

Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

[4-2] Method for producing polymer (C) (R2)
In this method, the hydrophilic polymer (B) polymerized in advance is bonded to the propylene polymer (A). In this case, as the hydrophilic polymer (B), those mentioned in (2) can be used.
Specifically, for example, when a hydrophilic monomer is first polymerized into a hydrophilic polymer, an unsaturated double bond is left in the molecule, and then a propylene polymer ( A) is a method of graft polymerization. In this case, as the propylene polymer (A), a propylene polymer (A2) having a reactive group can also be used, but a propylene polymer (A1) having no reactive group is usually used.

  Further, there is a method in which a hydrophilic polymer having a reactive group at the terminal is first polymerized, and then this is bonded to a propylene polymer (A2) having a reactive group. The hydrophilic polymer having a reactive group at the terminal can be obtained by polymerizing a hydrophilic monomer using a compound having a reactive group as an initiator or a chain transfer agent. Alternatively, it can also be obtained by ring-opening polymerization of a hydrophilic ring-opening polymerization monomer such as an epoxy compound.

As the hydrophilic monomer that can be used at this time, various hydrophilic monomers listed in [4-1] can be used in the same manner.
Any of these may be used alone or in combination of two or more.
The reaction method is not particularly limited as long as a polymer satisfying the requirements of the present invention can be produced, and any method may be used. Examples thereof include a method of reacting by heating and stirring in a solution, a method of reacting by melting and heating without solvent, and a method of reacting by heating and kneading with an extruder. The reaction temperature is usually in the range of 0 to 200 ° C, preferably in the range of 30 to 150 ° C. As a solvent in the case of manufacturing in a solution, the solvent quoted in [1-1] can be used similarly.

[5] Aqueous resin dispersion When the aqueous resin dispersion of the polymer (C) is produced, the production method is not particularly limited. For example, a solvent other than water is added to the polymer (C) described above, and necessary. A method of adding water to form a dispersion after heating and dissolving, and a method of adding water to form a dispersion after melting at a temperature at which the polymer (C) melts or higher are exemplified.

  The former is preferred. According to the method of preparing an aqueous dispersion by preparing a mixture of a polymer, water, and a solvent other than water and then removing the solvent from the mixture, an aqueous dispersion having a fine particle size can be easily produced. When preparing a mixture, you may heat as needed. The temperature is usually 30 to 150 ° C. The final ratio of the solvent other than water in the resin dispersion is usually 50% or less. It is preferably 20% or less, more preferably 10% or less, and particularly preferably 1% or less.

  Examples of the solvent other than water used in the present method include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, and alicyclic aliphatic systems such as cyclohexane and methylcyclohexane. Halogenated hydrocarbons such as hydrocarbons, methylene chloride, carbon tetrachloride, chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol and other alcohols, dipropyl alcohol Organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, etc. , Polar solvents such as dimethylformamide and dimethyl sulfoxide.

  Among them, a solvent that dissolves 1% by mass or more in water is preferable, and more preferably 5% by mass or more. For example, methyl ethyl ketone, methyl propyl ketone, cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol. , Isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol are preferred.

An apparatus for producing a water dispersion by adding water after the solvent is dissolved and melted is not particularly limited. For example, a reaction kettle with a stirring device, a uniaxial or biaxial kneader can be used. The stirring speed at that time varies slightly depending on the selection of the apparatus, but is usually in the range of 10 to 1000 rpm.
Since the polymer (C) of the present invention is very excellent in dispersibility in water, the water dispersion of the present invention has an advantage that the dispersed particle diameter is fine and the resin is stably dispersed. Therefore, when this is used, a coated product having an excellent appearance can be obtained.

  The solid content of the aqueous resin dispersion of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. Moreover, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The smaller the amount of solid content, the lower the viscosity, the easier it can be applied to various application methods and the higher the stability as a dispersion. However, for example, when used as a primer or an adhesive, it is preferable that the solid content is large so that a large amount of energy and time are not required for drying water after coating.

[5-1] Resin (D)
In the resin dispersion of the present invention, particles made of at least one resin (D) selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, epoxy resin, and vinyl ester resin are dispersed. It may be a resin that can be dispersed using a surfactant.
The volume average particle diameter of the particles made of the resin (D) is not particularly limited as long as the relationship with the volume average particle diameter of the polymer (C) described above is satisfied, but from the viewpoint of dispersion stability and the like, 0.01 μm to 1.0 micrometer is preferable, More preferably, it is 0.01 micrometer-0.5 micrometer, More preferably, it is 0.05 micrometer-0.5 micrometer.
In addition, when a dispersion containing particles made of the resin (D) is first prepared and combined with the dispersion containing the polymer (C) particles to form the resin dispersion of the present invention, the dispersion containing the resin (D) particles The resin solid content is preferably 15 to 70% by mass, more preferably 30 to 60% by mass. The liquid viscosity is preferably 1 to 50,000 mPa · s, more preferably 1 to 10,000 mPa · s, and still more preferably 10 to 10,000 mP · s.

Hereinafter, the resin (D) will be described in detail.
(D-1) Acrylic resin The acrylic resin of the present invention is not particularly limited as long as it is a (meth) acrylic polymer, but a homopolymer or copolymer of acrylic acid and / or an ester thereof, methacrylic acid and / or Or the homopolymer or copolymer of the ester. In addition, (meth) acryl refers to acryl and / or methacryl.

  Specific examples of the (meth) acrylate ester include (meth) acrylate ester monomers having an alkyl group having 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic Hexyl acid, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, or the like, or (Meth) acrylic acid ester having an aryl group or an aralkyl group having 6 to 12 carbon atoms, such as Meth) phenyl acrylate include benzyl (meth) acrylate and the like.

  Alternatively, (meth) acrylic acid esters having a C 1-20 alkyl group containing a hetero atom, such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid- 2-aminoethyl, (meth) acrylic acid glycidyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid hydroxybutyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3- Methoxypropyl, (meth) acrylic acid and polyethylene oxide adducts, etc., (meth) acrylic acid esters having a C 1-20 alkyl group containing a fluorine atom, such as trifluoromethyl methyl (meth) acrylate , (Meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic 2 Pa - fluoroethyl ethyl and the like, (meth) acrylamide monomers such as (meth) acrylamide, and the like (meth) acrylic dimethyl amide, respectively.

  In addition to the above (meth) acrylic acid and / or esters thereof, those having a double bond at the end of a molecule called a so-called macromonomer are also included. These (meth) acrylic macromonomers usually have a weight average molecular weight in the range of several hundred to 50,000. Such a (meth) acrylic oligomer is usually used in the range of 1 to 80 parts by mass per 100 parts by mass of the (meth) acrylic acid and / or its ester.

In addition to the above macromonomer, caprolactone-modified (meth) acrylic oligomer, terminal hydroxyl group-containing (meth) acrylic oligomer, oligoester (meth) acrylic oligomer, urethane (meth) acrylate, epoxy (meth) acrylate, etc. It is done.
In order to impart water resistance, heat resistance, solvent resistance, and chemical resistance to the acrylic resin, a crosslinkable functional group can be introduced and a crosslinking agent can be used in combination. For example, a copolymer having an epoxy group such as glycidyl (meth) acrylate and a polyfunctional carboxylic acid or polyfunctional amine as a crosslinking agent, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid hydroxybutyl, etc. A copolymer having a different hydroxyl group and a polyfunctional isocyanate, or a copolymer having a carbonyl group such as diacetone acrylamide or acrolein and a crosslinking system such as a polyfunctional hydrazine such as adipic acid dihydrazide or sebacic acid dihydrazide. be able to. Among these, a cross-linking system using a carbonyl group and a polyfunctional hydrazine is preferable because it can be stored at one temperature but can be cured at room temperature. These crosslinkable functional groups preferably have 0.5 parts by mass or more, more preferably 1 part by mass or more per 100 parts by mass of the acrylic resin. However, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the acrylic resin. The higher the lower limit value, the easier it is to obtain a sufficient crosslinking effect, and the lower the upper limit value, the higher the storage stability and the like.
Although it does not specifically limit as a polymerization method for manufacturing the above acrylic resins, For example, methods, such as solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, can be used.

To emulsify the acrylic resin obtained by solution polymerization or bulk polymerization into an aqueous emulsion to form an aqueous dispersion, emulsification and dispersion are carried out by mechanical force such as colloid mill in the presence or absence of the solution, and then necessary The residual solvent may be distilled off under reduced pressure or atmospheric pressure. If emulsion polymerization or suspension polymerization is used, the polymer can be obtained directly as an aqueous emulsion. A preferred form is an aqueous emulsion obtained by emulsion polymerization. Examples of commercially available products include Rikabond manufactured by Chuo Rika Kogyo Co., Ltd. and Acronal manufactured by BASF Japan Co., Ltd.
The acrylic resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 500,000 or less.

(D-2) Polyurethane resin The urethane resin of the present invention is not particularly limited. For example, (i) a component containing two or more active hydrogens in average in one molecule and (ii) a polyvalent isocyanate A urethane polymer obtained by reacting a component, or an isocyanate group-containing prepolymer obtained by reacting the component (i) and the component (ii) under an isocyanate group-excess condition and a chain extender such as a diol. The urethane polymer obtained by making it react is mentioned. These urethane polymers may contain an acid component (acid residue).

The chain extension method of the isocyanate group-containing prepolymer may be a known method. For example, water, a water-soluble polyamine, glycols or the like is used as the chain extender, and the isocyanate group-containing prepolymer and the chain extender component are used. May be reacted in the presence of a catalyst as necessary.
The component containing an average of 2 or more active hydrogens in one molecule of the component (i) is not particularly limited, but preferably has a hydroxylic active hydrogen. Specific examples of such compounds include the following.

  (1) Diol compound: ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5- Pentanediol, neopentyl glycol, 1,6-hexane glycol, 2,5-hexanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tricyclodecane dimethanol, 1,4- Cyclohexanedimethanol and the like.

  (2) Polyether diols: alkylene oxide adducts of the above diol compounds, ring-opening (co) polymers of alkylene oxides and cyclic ethers (tetrahydrofuran, etc.) such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol (block) Or random) copolymer, glycol, polytetramethylene glycol, polyhexamethylene glycol, polyoctamethylene glycol, and the like.

  (3) Polyester diol: Dicarboxylic acid (anhydride) such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, and ethylene glycol, propylene glycol as mentioned in (1) above , 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentylglycol and other diol compounds obtained by polycondensation under hydroxyl group-excess conditions. Specifically, ethylene glycol-adipic acid condensate, butanediol-adipine condensate, hexamethylene glycol-adipic acid condensate, ethylene glycol-propylene glycol-adipic acid condensate, or lactone is opened using glycol as an initiator. Examples thereof include polymerized polylactone diol.

  (4) Polyether ester diol: (anhydrous) dicarboxylic acid as exemplified in the above (3), an ether group-containing diol (polyether diol or diethylene glycol of (2) above) or a mixture of this with another glycol And a product obtained by reacting an alkylene oxide in addition to, for example, a polytetramethylene glycol-adipic acid condensate.

(5) Polycarbonate diol: General formula HO—R— (O—C (O) —O—R) _x —OH (wherein R is a saturated fatty acid diol residue having 1 to 12 carbon atoms, x is a molecular weight) The compound etc. which show the number of repeating units, and are the integers of 5-50 normally.). These include a transesterification method in which a saturated aliphatic diol and a substituted carbonate (diethyl carbonate, diphenyl carbonate, etc.) are reacted under the condition that the hydroxyl group is excessive, the saturated aliphatic diol and phosgene are reacted, or as necessary. Then, it can be obtained by a method of further reacting with a saturated aliphatic diol.

The compounds as exemplified in the above (1) to (5) can be used alone or in combination of two or more.
As the polyisocyanate component (ii) to be reacted with the component (i), an aliphatic, alicyclic or aromatic compound containing an average of two or more isocyanate groups in one molecule can be used.

  The aliphatic diisocyanate compound is preferably an aliphatic diisocyanate having 1 to 12 carbon atoms, and examples thereof include hexamethylene diisocyanate and 2,2,4-trimethylhexane diisocyanate. The alicyclic diisocyanate compound is preferably an alicyclic diisocyanate having 4 to 18 carbon atoms, and examples thereof include 1,4-cyclohexane diisocyanate and methylcyclohexylene diisocyanate. Examples of the aromatic isocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate.

  In addition, those containing acid residues in the urethane-based polymer can be dispersed in water without using a surfactant or in a small amount, so that the water resistance of the coating film is improved. There is expected. The content of the acid residue is preferably in the range of 25 to 150 (mgKOH / g), preferably 30 to 100 (mgKOH / g) as the acid value of the urethane polymer. If the acid value is less than 25, the water dispersibility tends to be insufficient, and it is often necessary to use a surfactant. On the other hand, if the acid value is more than 150, the water resistance of the coating film tends to be poor.

  As a method for introducing an acid group into a urethane polymer, a conventionally used method can be used without particular limitation. For example, dimethylolalkanoic acid is one of the glycol components described in the above (2) to (4). A method of introducing an acid group by introducing a carboxyl group into a polyether diol, a polyester diol, a polyether ester diol or the like in advance by substituting a part or all of them is preferable. Examples of the dimethylolalkanoic acid used here include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid. Examples of the commercially available products include Hydran and Bondick of Dainippon Ink Industries, Ltd., Superflex of Daiichi Pharmaceutical Industries, Ltd., and the like.

The urethane resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 200,000 or less.
When manufacturing the water dispersion of this urethane resin, the manufacturing method is not specifically limited, It can manufacture according to the manufacturing method of the water dispersion of the above-mentioned acrylic resin.

(D-3) Polyester resin The polyester resin of the present invention is not particularly limited, and examples thereof include dicarboxylic acids such as adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, and phthalic acid, and the like. / Or anhydrides thereof and diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentylglycol, or ether group-containing diols (polyethylene glycol) And polypropylene glycol, polytetramethylene glycol, and the like).

Specifically, there are ethylene glycol-adipic acid condensate, butanediol-adipine condensate, hexamethylene glycol-succinic acid condensate, ethylene glycol-propylene glycol-phthalic acid condensate, polyethylene glycol-adipic acid condensate, etc. .
An aqueous dispersion of a polyester resin can be obtained by emulsifying these in the presence or absence of a surfactant. Although the manufacturing method is not specifically limited, it can manufacture according to the manufacturing method of the aqueous dispersion of the above-mentioned acrylic resin. Examples of commercially available products include Vylonal MD-1200 and MD-1245 manufactured by Toyobo.
The polyester resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 5,000 or more. However, 500,000 or less is preferable, and more preferably 100,000 or less.

(D-4) Epoxy resin The epoxy resin of the present invention is not particularly limited as long as it is a polymer having one or more epoxy groups in one molecule. For example, by reacting polyhydric phenol with epichlorohydrin in the presence of alkali. Examples thereof include polyhydric glycidyl ethers of phenol that can be produced, and epoxy group-containing polymers obtained by reacting such polyhydric glycidyl ethers of phenol with the above polyhydric phenols.

  Examples of the polyhydric phenol that can be used here include bis (4-hydroxyphenyl) -2,2-propane, 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane, Bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-t-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, etc. Can be mentioned.

Instead of these polyhydric phenols, hydrogenated compounds obtained by adding hydrogen to part or all of the double bonds of the phenyl nucleus can also be used.
Further, as the epoxy resin, polyglycidyl ether of phenol novolac resin and polyglycidyl ether of polyhydric alcohol can also be used. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerol. , Bis (4-hydroxycyclohexyl) -2,2-propane, sorbitol and the like.

An aqueous dispersion of an epoxy resin can be obtained by emulsifying these in the presence or absence of a surfactant. Although the manufacturing method is not specifically limited, it can manufacture according to the manufacturing method of the aqueous dispersion of the above-mentioned acrylic resin.
As a typical product available as a commercial product, a de novolak type epoxy resin obtained by adding epichlorohydrin to a phenol novolac resin and forcibly emulsified with a surfactant (emulsifier) is a denar EM150 manufactured by Nagase Chemtech Co., Ltd. , Epiretz 6006W70, 5003W55 manufactured by Japan Epoxy Resin Co., Ltd., WEX-5100 manufactured by Toto Kasei Co., Ltd., and the like.
Similarly, bisphenol-type epoxy resin obtained by adding epichlorohydrin to bisphenol was forcibly emulsified with an emulsifier. 3540WY55 etc. are mentioned.

Furthermore, as an alkyl type epoxy resin in which epichlorohydrin is added to a polyol such as sorbitol, pentaerythritol, glycerin, etc., Denars EX-611, EX-614, EX-411, EX-313 manufactured by Nagase Chemtech Co., Ltd. and the like can be mentioned.
The epoxy resin of the present invention preferably has a number average molecular weight of 1,000 or more, more preferably 20,000 or more. However, it is preferably 1,000,000 or less, more preferably 200,000 or less.

(D-5) Vinyl ester-based resin The vinyl ester-based resin of the present invention is a copolymer containing a vinyl ester single polymer or a polymer of a vinyl ester monomer and another radical polymerizable monomer. is there. Examples of the radical polymerizable monomer include ethylene, (meth) acrylic acid ester, aromatic vinyl, unsaturated nitrile, acrylamide, (meth) acrylic acid, α, β-unsaturated dicarboxylic acid and the like.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acid having 8 to 10 carbon atoms, so-called vinyl versatate (for example, trade name: Veova 10 manufactured by Shell Chemical Co., Ltd.) And alkyl acid vinyl esters. Of these, vinyl acetate is preferable, and the vinyl ester resin is particularly preferably a vinyl acetate homopolymer or an ethylene-vinyl acetate copolymer.

  The mass ratio between the ethylene unit and the vinyl ester unit in the copolymer is preferably in the range of 5 to 70 parts by mass of the ethylene unit contained in the polymer when the vinyl ester unit is 100 parts by mass. 10-50 mass parts is more preferable. When the ethylene unit is more than 5 parts by mass, the initial adhesiveness and water resistance are improved, and when it is less than 70 parts by mass, the adhesive strength tends to be improved.

  A copolymer emulsion can be usually produced by emulsion polymerization of the monomers constituting the ethylene units and vinyl ester units. Examples of the emulsifier used in the emulsion polymerization include water-soluble polymer compounds such as hydroxymethyl cellulose and carboxymethyl cellulose, and protective colloids such as partially saponified or completely saponified polyvinyl acetate emulsifiers. In the present invention, the partially saponified polyvinyl acetate emulsifier is used. Among these partially saponified polyvinyl acetate emulsifiers, those partially saponified at an average polymerization degree of about 100 to 3000 and an average saponification degree of 80 to 98 mol% are more preferable.

  Specific examples of the vinyl ester resin emulsion include Sumikaflex 400, 401, 305, 455, 500, 510, 700, 751, 900 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000, OM-4200. (Above, manufactured by Kuraray Co., Ltd.), Polysol EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59, P-900 (above, Showa Polymer ( Co., Ltd.), Denka EVA-Tex # 20, # 30, # 40M, # 60, # 81, # 82 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), etc., commercially available aqueous emulsions of ethylene-vinyl ester copolymers May be used as they are.

[5-2] Surfactant The resin dispersion of the present invention has a surfactant content of 10 parts by mass or less with respect to 100 parts by mass of the resin component (total amount of the polymer (C) and the resin (D)). . That is, the dispersed particle size of the polymer (C) is very small, but contains very little or substantially no surfactant. Thereby, when this resin dispersion is used as a coating material, there is an advantage that a bleed-out can be suppressed and a coated product excellent in appearance can be obtained, and this resin dispersion can be used as a coating material on the outermost surface of coating. In addition, the water resistance and oil resistance (GH resistance) of the coating can be improved, and the resulting resin dispersion has any of adhesion, water resistance, moisture resistance, oil resistance (GH resistance), and chemical resistance. Will also be excellent.

  A smaller amount of the surfactant is preferable, and the surfactant content of the resin dispersion is preferably 5 parts by mass or less with respect to 100 parts by mass of the resin component. More preferably, it is 3 mass parts or less, More preferably, it is 2 mass parts or less. It can also be substantially free of surfactant. “Substantially no surfactant” means less than 1 part by mass with respect to 100 parts by mass of the total amount of resin components.

  As the surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant and the like can be used. As the surfactant, those having an alkyl group, alkenyl group, alkylaryl group or alkenylaryl group having 4 or more carbon atoms as a hydrophobic group are usually used. Preferably it is C8 or more, More preferably, it is C12 or more. However, it usually has 30 or less carbon atoms.

  Examples of the nonionic surfactant include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, and the like. Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium sulfosuccinate, sodium lauryl sulfate, and sodium polyoxyethylene lauryl sulfate. Examples of the cationic surfactant include stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and the like. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine.

Moreover, what is called a reactive surfactant etc. in which said surfactant has a radically polymerizable functional group can also be used. When a reactive surfactant is used, the water resistance of a film formed using this resin dispersion can be improved. Typical commercially available reactive surfactants include Eleminol JS-2 (manufactured by Sanyo Chemical Industries) and Latemuru S-180 (manufactured by Kao).
In addition, since nonionic surfactant is hard to reduce water resistance compared with other surfactant, nonionic surfactant may be included a little more. For example, when the surfactant other than the nonionic surfactant should be 5 parts by mass or less with respect to 100 parts by mass of the polymer (C), the nonionic surfactant may be 10 parts by mass or less.
Further, according to the present invention, it is not always necessary to use chlorinated polyolefin, and there is an advantage that the environmental load can be reduced.

[5-3] Addition of pigment Pigment (E) can be added to the resin dispersion of the present invention. The aqueous resin dispersion containing the pigment (E) is suitable as a paint.
The pigment that can be used is not particularly limited. For example, inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, and perinone pigments. , Perylene pigments, quinacridone pigments, isoindolinone pigments, indigo pigments, organic pigments such as phthalocyanine pigments, etc .; extenders such as talc, calcium carbonate, clay, kaolin, silica, precipitated barium sulfate ; Conductive pigments such as whiskers coated with conductive carbon and antimony-doped tin oxide; non-colored or colored metallic luster such as aluminum, copper, zinc, nickel, tin, aluminum oxide, or other metals or alloys 1 type, or 2 or more types may be used in combination.

  The amount of the pigment (E) added to the resin dispersion is preferably 10 parts by mass or more with respect to 100 parts by mass of the resin (total amount of the polymer (C) and the resin (D)). More preferably, it is 50 parts by mass or more. However, 400 mass parts or less are preferable, More preferably, it is 200 mass parts or less. As the addition amount is larger than the lower limit value, the color developability and the hiding property tend to be higher, and as the addition amount is smaller than the upper limit value, the adhesion, moisture resistance and oil resistance tend to be higher.

  At this time, a pigment dispersant may be used. For example, an aqueous acrylic resin such as Jonkrill Resin manufactured by Johnson Polymer Co., Ltd .; an acidic block copolymer such as BYK-190 manufactured by BYK Chemie Co., Ltd .; a styrene-maleic acid copolymer; manufactured by Air Products (Air Products Co., Ltd.) Examples thereof include acetylenic diol derivatives such as Surfynol T324; water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Company. By using these pigment dispersants, a stable pigment paste can be prepared.

  As a production method for dispersing the pigment (E) in the resin dispersion of the present invention, a known method can be used, and is not particularly limited. For example, pigment and water, other pigment dispersant, thickener, antifoaming agent in advance. Etc. may be mixed to prepare a pigment base, and then the pigment base and the aqueous resin dispersion may be mixed. If necessary, a freeze / thaw stabilizer, a film-forming aid, a preservative, a fungicide, and the like may be blended. Or you may mix a pigment, water, an aqueous resin dispersion, and the said other additive simultaneously. For mixing, a mixer such as a dissolver, a homogenizer, or a homomixer, or a disperser such as a paint shaker, a ball mill, a sand mill, an attractor, a roll mill, or a kneader can be used.

[5-4] Other Additives An acidic substance or a basic substance can be added to the resin dispersion of the present invention as necessary. Examples of the acidic substance include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Examples of basic substances include inorganic bases such as sodium hydroxide and potassium hydroxide, triethylamine, diethylamine, diethylethanolamine, and 2-methyl-2-amino-propanol.

  In addition, various additives may be included as necessary within a range that does not significantly impair the effects of the present invention. For example, various stabilizers such as ultraviolet absorbers, antioxidants, weathering stabilizers, heat resistance inhibitors, etc .; conductivity imparting agents such as carbon black and ferrite, dyes, pigment dispersants, leveling agents, antifoaming agents, Various additives such as a sticking agent, an antiseptic, a fungicide, a rust inhibitor, and a wetting agent may be used in combination.

Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.
To further improve the performance of various coatings such as water resistance and solvent resistance. The crosslinking agent can be added in an amount of 0.01 to 100 parts by mass with respect to 100 parts by mass of the resin in the dispersion. As the crosslinking agent, there can be used 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, etc. Among them, an isocyanate compound, 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.

  When the resin dispersion of the present invention is used for applications such as primers and paints, a hydrophilic organic solvent other than water can be blended for the purpose of increasing the drying speed or obtaining a surface with a good finish. Examples of the hydrophilic organic solvent include alcohols such as methanol and ethanol, ketones such as acetone, glycols such as ethylene glycol and propylene glycol, and ethers thereof, N-methylpyrrolidone, and the like. Preferred are isopropanol, ethanol, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and N-methylpyrrolidone. These contents are usually 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of water and the organic solvent.

  The aqueous resin dispersion of the present invention can be used for a primer, a primerless paint, an adhesive, and the like, and can be particularly useful as a paint. The paint is applied to the surface of an object to be colored, and for protection and adhesion, and is a concept including so-called ink. This paint is particularly suitable for polyolefin substrates, especially propylene polymer substrates. For example, it can be used for automotive paints for automobile interiors and exteriors, primers, paints for home appliances such as mobile phones and personal computers, paints for building materials, gravure inks, offset inks and the like.

[6] Laminate A resin layer can be formed by applying the resin dispersion of the present invention or a paint containing the same to a substrate and heating it to form a laminate. This resin layer comprises at least one resin (D) selected from the group consisting of a polymer (C) containing a propylene polymer (A), an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl ester resin. ) At a mass ratio of 90:10 to 10:90 of (A) :( D), and the surfactant content is 10 parts by mass with respect to 100 parts by mass of the total amount of the polymer (C) and the resin (D). It is the following layer.

This laminate can be used in various applications such as for automobiles, home appliances, and building materials. The substrate may be in any shape, such as a film, sheet, or plate.
The resin dispersion of the present invention can be applied to a crystalline olefin polymer molding (base material) to form a coating film. Examples of the olefin polymer as a base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene, and other olefin polymers, ethylene / propylene copolymer. Examples thereof include olefin copolymers such as polymers, ethylene / butene copolymers, and propylene / butene copolymers. Of these olefin copolymers, propylene-based polymers are preferably used. Also, molded articles made of polypropylene and synthetic rubber, molded articles made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, etc., such as molded articles such as bumpers for automobiles, and for steel plates and electrodeposition treatment It can also be used for surface treatment of steel plates and the like.

In addition, the molded body to which the resin dispersion of the present invention is applied is formed by any of the above-described various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. It may be what was done.
A coating film with good adhesion can also be formed when these molded bodies are blended with inorganic fillers such as talc, zinc white, glass fiber, titanium white, and magnesium sulfate, and pigments.

[6-1] Method for Producing Laminate A method for forming a resin layer on a substrate is not particularly limited, and any known method can be used. For example, a resin dispersion or a paint is spray-coated, a bar Examples of the method include coating by various methods such as coating, spin coating, dip coating, and gravure coating. In general, coating by spray coating is applied to large molded bodies such as automobile bumpers and home appliances, and coating by gravure coating or bar coating is performed on plastic films and sheets.

After applying the resin dispersion or paint, it is usually heated with nichrome wire, infrared rays, high frequency or the like to cure the coating film, thereby obtaining a laminate having a desired coating film on the surface. The curing conditions for the coating film are appropriately selected depending on the material and shape of the substrate, the composition of the paint used, and the like. Although there is no restriction | limiting in particular in hardening temperature, Considering practicality, it is 50 degreeC or more normally, Preferably it is 60 degreeC or more. However, it is usually 150 ° C. or lower, preferably 130 ° C. or lower.
The thickness of the resin layer to be laminated (after curing) can be appropriately selected depending on the material and shape of the substrate, the composition of the paint used, etc., but is usually 0.1 μm or more, preferably 1 μm or more, more preferably 5 μm. That's it. However, it is usually 500 μm or less, preferably 300 μm or less, more preferably 200 μm or less, and particularly preferably 100 μm or less.

[6-2] Thermoplastic resin molding (F)
The base material of the laminate of the present invention is preferably a thermoplastic resin molded body. Although it does not specifically limit as a thermoplastic resin molded object (F), For example, it is a molded object which consists of polyolefin resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin etc. In particular, the present invention is preferably applied to a thermoplastic resin molded product (F) made of a polyolefin resin, and in particular, a thermoplastic resin molded product (F) made of a propylene-based polymer (hereinafter referred to as a propylene-based polymer molded product). It is preferable to apply to.

  The propylene-based polymer molded body is usually a molded body of a crystalline propylene-based polymer, and a known one can be used, and is not particularly limited. For example, a homopolymer of propylene, propylene and other comonomers such as ethylene , Butene-1, pentene-1, hexene-1, heptene-1, octene-1, cyclopentene, cyclohexene, and a copolymer with one or more α-olefin comonomers having 2 or more carbon atoms such as norbornene Can do.

  The α-olefin comonomer is preferably an α-olefin comonomer having 2 to 6 carbon atoms. Copolymers of α-olefin monomers and comonomers such as vinyl acetate, acrylic acid esters and methacrylic acid esters, copolymers of comonomers such as aromatic vinyl monomers or hydrogenated products thereof, and conjugated diene block copolymers A hydrogenated product or the like can also be used. In addition, when only calling it a copolymer, it may be a random copolymer or a block copolymer. Further, the propylene polymer may be modified as necessary.

These can be used alone or as a mixture depending on the application.
The propylene polymer preferably has a melt flow rate (MFR) of 2 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, and particularly preferably 25 g / 10 minutes. However, it is preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less. When MFR is higher than the lower limit, the flowability of the propylene polymer tends to increase. Conversely, if the MFR is lower than the upper limit value, the mechanical properties tend to increase. The MFR of the propylene-based polymer may be adjusted at the time of polymerization, or may be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide after the polymerization.

  More preferably, the propylene polymer is crystalline polypropylene. Crystalline polypropylene is a propylene homopolymer and / or a propylene / ethylene copolymer. Here, the propylene / ethylene copolymer is a propylene / ethylene random copolymer and / or a propylene / ethylene block copolymer, and preferably a propylene / ethylene block copolymer.

Here, the propylene / ethylene block copolymer is composed of a crystalline polypropylene part (a unit part) and an ethylene / propylene random copolymer part (b unit part).
The a unit is usually obtained by homopolymerization of propylene, and in some cases, by copolymerizing a small amount of other α-olefin with propylene.
The MFR of the polypropylene homopolymer of a unit part is preferably 10 g / 10 minutes or more, more preferably 15 g / 10 minutes or more, still more preferably 20 g / 10 minutes or more, and particularly preferably 40 g / 10 minutes or more. . However, it is preferably 500 g / 10 min or less, more preferably 400 g / 10 min or less, still more preferably 300 g / 10 min or less.

As this MFR is higher than the lower limit, the flowability tends to increase. Conversely, the mechanical properties tend to increase as the MFR is lower than the upper limit.
On the other hand, the b unit is a rubbery component obtained by random copolymerization of propylene and ethylene.
The propylene content of the propylene / ethylene random copolymer part of the b unit part is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. However, it is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. When the propylene content is within this range, the dispersibility and glass transition temperature are within an appropriate range, and impact characteristics tend to be good. The propylene content can be adjusted by controlling the concentration ratio of propylene and ethylene during the polymerization of the propylene / ethylene random copolymer portion.

The molecular weight of the propylene / ethylene random copolymer part of the b unit part is not particularly limited, but in consideration of dispersibility and impact resistance, the weight average molecular weight (Mw) is preferably 200,000 to 3,000,000, more preferably Is 300,000-2,500,000, more preferably 400,000-2 million.
Although there is no restriction | limiting in particular about the quantity of a unit part and b unit part, Generally a unit part becomes like this. Preferably it is 95 mass% or less of the whole quantity, More preferably, it is 50-95 mass%, More preferably, it is 60-90 mass%. , B unit part is preferably adjusted to 5% by mass or more of the total amount, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass. The impact resistance characteristics tend to increase as the amount of b unit part is equal to or greater than the lower limit, and the rigidity, strength, and heat resistance tend to increase as the amount is less than the upper limit.

In the present invention, the amount of b unit part is measured using a temperature rising elution fractionation method. That is, the a unit part does not elute at 100 ° C. or lower in the extraction with orthodichlorobenzene, but the b unit part elutes easily. Therefore, the composition of the propylene / ethylene block copolymer after production is determined by extraction analysis using the orthodichlorobenzene.
Since the ratio of the amount of the a unit part to the b unit part is determined by the polymerization amount of the propylene homopolymer part and the polymerization amount of the propylene / ethylene random copolymer part, it can be adjusted by controlling the respective polymerization times.

The production method of the propylene homopolymer or the propylene / ethylene block copolymer is not particularly limited, and is appropriately selected from known methods and conditions.
As the propylene polymerization catalyst, a highly stereoregular catalyst is usually used. For example, a catalyst comprising a combination of a titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating with various electron donors and electron acceptors, an organoaluminum compound and an aromatic carboxylic acid ester ( JP-A 56-1000080, JP-A 56-120712, JP-A 58-104907), and a supported type in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide. Examples thereof include catalysts (see JP-A-57-63310, JP-A-63-43915, and JP-A-63-83116). Furthermore, a metallocene catalyst as shown in WO91 / 04257 and the like can also be mentioned. The metallocene-based catalyst may not contain alumoxane, but is preferably a so-called Kaminsky-based catalyst in which a metallocene compound and an alumoxane are combined.

  The propylene / ethylene block copolymer is obtained by first polymerizing propylene alone in the presence of the above catalyst by applying a production process such as a gas phase polymerization method, a liquid phase bulk polymerization method, or a slurry polymerization method, and then propylene and ethylene. Can be obtained by random polymerization. In order to obtain a propylene / ethylene block copolymer having the above-described melting characteristics (MFR), it is preferable to perform multistage polymerization using a slurry method or a gas phase fluidized bed method. Alternatively, it can be obtained by a method in which propylene homopolymerization is performed in multiple stages and then propylene and ethylene are randomly polymerized. When producing a propylene / ethylene block copolymer having a large number of b units, the gas phase fluidized bed method is particularly preferred.

The propylene homopolymer is obtained by polymerizing propylene alone in the presence of the catalyst by applying a production process such as a phase polymerization method, a liquid phase bulk polymerization method, a slurry polymerization method or the like. In order to obtain a propylene homopolymer having the above-described melting characteristics (MFR), it is preferable to perform multistage polymerization using a slurry method or a gas phase fluidized bed method.
The propylene homopolymer and propylene / ethylene block copolymer of the present invention preferably have excellent mechanical properties and high rigidity and impact resistance in order to be used as a structural material. That is, the flexural modulus is preferably 300 MPa or more, more preferably 500 to 3000 MPa, and still more preferably 1000 to 2000 MPa. By being in this range, it will be excellent in rigidity and suitable as a structural material. The IZOD impact strength is preferably 1 kJ / m ² or more, more preferably ^{2 to} 100 kJ / m ² , still more preferably 5 to 80 kJ / m ² , and particularly preferably 8 to 60 kJ / m ² . By making it within this range, it has excellent impact resistance and is suitable as a structural material.
A thermoplastic resin molding may be used individually by 1 type, and may be used in combination of 2 or more type.

[6-3] Inorganic filler component The thermoplastic resin molded product (F) used in the present invention may contain an inorganic filler component.
In particular, mechanical properties such as bending elastic modulus and rigidity of the molded body can be improved by blending the crystalline polyolefin with an inorganic filler component.
Specifically, plate fillers such as talc, mica and montmorillonite; fiber fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber and zonolite; potassium titanate, magnesium Needle-shaped fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Granular fillers; balun fillers such as glass balloons; Inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate can also be used. Of these, talc, mica, glass fiber, and whisker are preferable from the balance between physical properties and cost, and talc, mica, and glass fiber are more preferable.

The inorganic filler component may be surface-treated with a surfactant, a coupling agent or the like. The surface-treated filler has an effect of further improving the strength and heat-resistant rigidity of the molded product.
The amount of the inorganic filler component used is selected from a wide range depending on the purpose and application of the molded article, but is preferably 1 to 80 parts by mass, more preferably 2 to 75 parts by mass, and more preferably 100 parts by mass of the crystalline polyolefin. Preferably it is 5-60 mass parts.

By including the inorganic filler component, the flexural modulus of the crystalline polyolefin can be improved to preferably 1000 MPa or more, more preferably 1500 to 10000 MPa, and still more preferably 2000 to 8000 MPa. The IZOD impact strength can be improved to preferably 1 kJ / m ² or more, more preferably ^{2 to} 80 kJ / m ² , and further preferably 4 to 60 kJ / m ² .
An inorganic filler component may be used individually by 1 type, and may be used in combination of 2 or more type.

Hereinafter, preferred fillers will be described in detail.
(1) Talc The average particle diameter of talc used in the present invention is usually 10 μm or less, preferably 0.5 to 8 μm, more preferably 1 to 7 μm. The average particle size value is a cumulative amount obtained by drawing a particle size cumulative distribution curve from a measurement result obtained by a laser diffraction method (for example, LA920W manufactured by Horiba, Ltd.) or a liquid layer sedimentation method light transmission method (for example, CP type manufactured by Shimadzu Corp.). The particle size value is 50% by mass. The value in the present invention is an average particle diameter value measured by a laser diffraction method.

As the talc, fine particles obtained by further finely classifying naturally produced talc obtained by mechanically pulverizing the talc are used. What was once coarsely classified may be further classified.
Examples of the mechanical crushing method include a method using a crusher such as a jaw crusher, a hammer crusher, a roll crusher, a screen mill, a jet crusher, a colloid mill, a roller mill, and a vibration mill. In order to adjust the pulverized talc to the above average particle size, wet or dry classification is performed once or repeatedly in an apparatus such as a cyclone, a cyclone air separator, a micro separator, or a sharp cut separator.

As a method for producing talc of the present invention, it is preferable to perform a classification operation with a sharp cut separator after pulverization to a specific particle size.
These talcs are modified polyolefins, fatty acids grafted with various organic titanate coupling agents, organic silane coupling agents, unsaturated carboxylic acids or anhydrides for the purpose of improving the adhesion or dispersibility with the polymer. The surface treatment may be performed with a fatty acid metal salt, a fatty acid ester, or the like.

(2) Glass fiber It is common to use glass chopped strand as glass fiber. The length of the glass chopped strand is usually 3 to 50 mm, and the fiber diameter is usually 3 to 25 μm, preferably 8 to 14 μm.
As the glass chopped strand, it is preferable to use a surface-modified one with a silane compound or a surface treatment with a sizing agent such as polyvinyl alcohol, polyvinyl acetate, polyurethane, epoxy resin, or olefin component.

Examples of the olefinic component as the sizing agent include unsaturated carboxylic acid-modified polyolefins and low molecular weight polyolefins.
In the present invention, a polyolefin modified with an unsaturated carboxylic acid and / or a derivative thereof may be blended in order to improve mechanical strength by interfacial adhesion between the crystalline polyolefin and the glass fiber. In particular, those obtained by modifying polypropylene as a base material are preferable, and those having a modification rate of 0.1 to 10% by mass are preferably used.

(3) Mica Mica preferably has an average particle diameter of 2 to 100 μm and an average aspect ratio of 10 or more, more preferably an average particle diameter of 2 to 80 μm and an average aspect ratio of 15 or more. When the average particle diameter of the mica is within the above range, the scratch resistance and impact strength of the molded product can be further improved, and deterioration of the appearance can be suppressed.

The mica may be any of so-called white mica, gold mica, black mica, etc., but gold mica and white mica are preferable, and white mica is more preferable.
The method for producing mica is not particularly limited and is produced by a method according to the above-mentioned talc. However, dry pulverization / wet classification or wet pulverization / wet classification is preferable, and wet pulverization / wet classification is more preferable.

[6-4] Elastomer Component When the thermoplastic resin molded product (F) used in the present invention is a crystalline polyolefin molded product, an elastomer component can be further contained. Thereby, the impact strength of the molded product can be improved.
Examples of the elastomer component include ethylene-α-olefin random copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber, and styrene-containing thermoplastic elastomer. Specific examples include ethylene-α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-hexene copolymer rubber, and ethylene-1-octene copolymer rubber. Polymer rubber; ethylene-α-olefin-nonconjugated diene copolymer rubber such as ethylene-propylene-ethylidene norbornene copolymer rubber (EPDM); hydrogenated product of styrene-butadiene-styrene triblock (SEBS), styrene -Styrene-containing thermoplastic elastomer such as hydrogenated product (SEPS) of isoprene-styrene triblock body can be exemplified.

These elastomers can be produced as follows.
The MFR (230 ° C., 2.16 kg load) of these elastomer components is preferably 0.5 to 150 g / 10 minutes, more preferably 0.8 when considering an automobile exterior material which is one of the main uses of the present invention. It is 7 to 100 g / 10 minutes, and more preferably 0.7 to 80 g / 10 minutes.
An elastomer component may be used individually by 1 type, and may be used in combination of 2 or more type.

[6-5] Other components In addition to the above, the thermoplastic resin molded article (F) can contain arbitrary additives and blending components as long as the effects of the present invention are not significantly impaired. Specifically, pigments for coloring, antioxidants such as phenols, sulfurs and phosphoruss, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, various nucleating agents such as organic aluminum and talc, dispersion Agents, neutralizers, foaming agents, copper damage inhibitors, lubricants, flame retardants, and other resins such as polyethylene resins.

[6-6] Method for Producing Thermoplastic Resin Molded Body (F) Various components are blended into the resin described above as necessary, and mixed and melt-kneaded. The kneading method is not particularly limited, and the heat of the present invention is obtained by kneading and granulating using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader. The thermoplastic resin composition which comprises a plastic resin molding (F) is obtained. In order to improve the dispersion of each component, a twin screw extruder is preferably used.

In this kneading and granulation, the above components may be kneaded at the same time, or a method of dividing and kneading each component in order to improve performance may be employed.
Next, the thermoplastic resin composition is molded to obtain a thermoplastic resin molded body (F), and various known methods can be used as the molding method.
Examples include injection molding (including gas injection molding), compression molding, injection compression molding (press injection), extrusion molding, hollow molding, rotational molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, and the like. It is done. Preferably, injection molding, compression molding, and injection compression molding are used, and injection molding is particularly preferable in consideration of productivity and the like.

[6-7] Use of Laminate The laminate of the present invention is excellent in coating film adhesion and further has a physical property balance excellent in rigidity and impact resistance. Moreover, when the resin layer which comprises a laminated body does not contain surfactant substantially, since a bleedout does not arise, it is excellent also in an external appearance. Moreover, since it is not necessary to contain halogens, such as chlorine, environmental impact can be reduced.
Therefore, the laminate of the present invention can be used for various industrial parts such as automobiles, home appliances, and building materials, and in particular, has sufficient performance for practical use as thinned, highly functional, and enlarged parts / materials. .
For example, automotive parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tanks, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, toilet seat lids, water tanks and other toiletry parts, It can be used as a molding material for various industrial parts such as parts around the bathroom such as a bathtub, bathroom wall, ceiling, and drain pan.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded. Unless otherwise stated,% represents mass%.
<Physical property measurement method and evaluation method>
(1) Stereoregularity The stereoregularity [mmmm] of polypropylene was measured by a ¹³ C-NMR spectrum measurement method using an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a flip angle of 90 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value of the spin lattice relaxation time of the methyl group). In the propylene-based polymer, since the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group, the recovery of the magnetization of all the carbons is 99% or more under this measurement condition. Measurement was carried out by integrating over 20 hours.

(2) Molecular weight First, 20 mg of a sample was collected in a 30 ml vial, and 20 g of orthodichlorobenzene containing 0.04% by mass of BHT was added as a stabilizer. After dissolving the sample using an oil bath heated to 135 ° C., it was filtered hot with a PTFE (polytetrafluoroethylene) filter having a pore diameter of 3 μm to prepare a sample solution having a polymer concentration of 0.1% by mass. Next, GPC measurement was performed by using TSKgel GM H-HT (30 cm × 4) as a column and Waters GPC150CV equipped with an RI detector. As measurement conditions, a sample solution injection amount: 500 μl, a column temperature: 135 ° C., a solvent: orthodichlorobenzene, and a flow rate: 1.0 ml / min were employed.

When calculating the molecular weight, use a commercially available monodisperse polystyrene as a standard sample, create a calibration curve for retention time and molecular weight from the polystyrene standard sample and the viscosity formula of polypropylene, and calculate the molecular weight of the propylene-based polymer. went.
[Η] = K · Mα is used as the viscosity formula, K = 1.38E-4 and α = 0.70 for polystyrene, and K = 1.03E- for propylene-based copolymers. 4, α = 0.78 was used.

(3) Graft rate 200 mg of the polymer and 4800 mg of chloroform are put into a 10 ml sample bottle and heated at 50 ° C. for 30 minutes to be completely dissolved. Chloroform was placed in a liquid cell having a material NaCl and an optical path length of 0.5 mm as a background. Next, the dissolved polymer solution was put into a liquid cell, and an infrared absorption spectrum was measured using FT-IR460plus manufactured by JASCO Corporation at a total number of 32 times. The graft ratio of maleic anhydride was calculated using a calibration curve prepared by measuring a solution of maleic anhydride in chloroform. Then, from the area of the absorption peak of the carbonyl group (maximum peak near 1780 cm ⁻¹ , 1750 to 1813 cm ⁻¹ ), the acid component content in the polymer is calculated based on a separately prepared calibration curve, and this is calculated as the graft ratio ( Mass%).

(4) Dispersion particle diameter It measured using Microtrac UPA (batch type dynamic light scattering method / laser Doppler method) by Nikkiso Co., Ltd. Measured at a measurement time of 120 seconds with the density of the dispersion being 0.9 g / cm ³ , the particle shape being a true sphere, the refractive index of the particle being 1.50, the dispersion medium being water and the refractive index of the dispersion medium being 1.33. The volume average particle size (50% particle size) and 90% particle size were determined.

(5) Foaming property 10 g of a sample is placed in a 30 ml sample bottle and vigorously stirred for 1 minute in a paint shaker. The sample bottle was allowed to stand, and the state of bubbles was visually confirmed after 3 minutes.
○: No bubbling or slight x: Bubbling severe

(6) Initial adhesion The board | substrate which made the injection molding of 70 mm x 150 mm x 3 mm the grade for the automobile interior grade polypropylene was created, and the substrate surface was wiped with isopropyl alcohol. Here, the sample was spray coated so that the dry weight after coating was about 15 g / m ² . Next, the coated test piece was baked at 70 ° C. for 20 minutes in a safe ben dryer to obtain a coated plate.
After leaving at 23 ° C. for 24 hours, a test piece having a grid of 25 squares (5 × 5) was prepared at intervals of 2 mm in accordance with the grid test method described in JIS K 5400, and cellophane tape (Nichiban) After attaching the product, it was peeled in the direction of 90 degrees, and the evaluation was made based on the number of grids that were not peeled out of 25 grids.

(7) Bleed-out A coated plate prepared in the same manner as the initial adhesion test is left at 40 ° C. for 3 days to determine the state of the surfactant that bleeds out to the coating surface visually and by touch. did.
○: No bleed-out of surfactant △: Slightly bleed-out surfactant ×: Surfactant is bleed-out and sticky when touched with a finger

(8) Moisture resistance A coated plate prepared in the same manner as in the initial adhesion test was left in a state of 50 ° C. and a relative humidity of 95% for 1 week, and the appearance of the coating was visually determined. Further, a cross-cut test was performed in the same manner as in the case of the initial adhesion test, and the evaluation was performed based on the number of cross-cuts that were not peeled out of the 25 cross-cuts.

(9) Beef tallow resistance Beef tallow (Wako Pure Chemicals / reagent grade) was applied to a coated plate prepared in the same manner as in the initial adhesion test so that the application amount was about 2 g / 100 cm ^2, and the temperature was 1 at 80 ° C. Left for days. After the beef tallow applied on the surface was washed with a neutral detergent, the appearance of the coating film was visually determined.
○: Good ×: Swelling and tearing of the coating film are observed

<Substance used>
MD-1200: Byonal MD-1200 manufactured by Toyobo Co., Ltd. (aqueous polyester resin dispersion, solid content concentration 35%, resin Tg: 67 ° C., average particle size: 0.08 μm)
BD-2250: Bonded 2250 manufactured by Dainippon Ink Co., Ltd. (aqueous polyurethane resin dispersion, resin solid content 35%, average particle size: 0.105 μm)
ES-20: Rikabond ES-20 manufactured by Chuo Rika Kogyo Co., Ltd. (aqueous acrylic resin dispersion, solid content concentration 44%, resin Tg: 47 ° C., average particle size: 0.10 μm)
EH-801: Hardylene EH-801 manufactured by Toyo Kasei Co., Ltd. (aqueous chlorinated propylene polymer resin dispersion, solid content concentration 30%, average particle size: 0.036 μm, amount of surfactant: 30% by mass)
Thickener 636 (thickener): SN thickener 636 manufactured by San Nopco

[Production Example 1: Production of polypropylene]
In a 1,000 ml round bottom flask, 110 ml of demineralized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved with stirring. In this solution, 16.7 g of commercially available granulated montmorillonite (Mizusawa Chemical Benclay SL) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The recovered cake was slurried again with 500 ml of demineralized water in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.

To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To this suspension was added 80 ml of toluene, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In another flask, 0.2 mmol of triisobutylaluminum (manufactured by Tosoh Akzo) was collected, and 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H A toluene diluted solution of 131 mg (57 μmol) of 5,6,7,8-tetrahydro-1-azulenyl) hafnium was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry. 002310).

  Next, 11 L of toluene, 3.5 mmol of triisobutylaluminum and 2.64 L of liquid propylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 63 ° C., and the total pressure during polymerization was kept constant at 0.65 MPa, and stirring was continued for 2 hours at the same temperature. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and clay residue were removed. As a result, 11 kg (1.4 kg propylene polymer) of a 12.8% by mass propylene polymer toluene solution was obtained. The resulting polypropylene had a weight average molecular weight Mw of 180,000 and stereoregularity [mmmm] of 47.5%.

[Production Example 2: Production of maleic anhydride-modified polypropylene]
350 g of the polypropylene obtained in Production Example 1 and 650 g of toluene were placed in a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, and the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After raising the temperature, 17.5 g of maleic anhydride was added, 8.75 g of t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, Perbutyl I) was added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a maleic anhydride-modified polymer in the form of a white powder. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.2% by mass (0.12 mmol / g). The weight average molecular weight was 110,000.

[Production Example 3: Production of polyalkylene glycol-modified polypropylene aqueous resin dispersion]
In a glass flask equipped with a reflux condenser, thermometer, and stirrer, 30 g of maleic anhydride-modified polypropylene synthesized in Production Example 2 (maleic anhydride group content 3.6 mmol) and 70 g of toluene were added, and the temperature was adjusted to 110 ° C. The temperature was raised and the solution was completely dissolved. Next, 7.5 g (7.5 mmol, 100 parts by mass of a propylene-based polymer) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyether amine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value)) (Corresponding to 25 parts by mass) was added to a solution of 7.5 g of toluene and reacted at 110 ° C. for 3 hours.

After cooling, toluene was distilled off under reduced pressure to obtain 37 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, the peak corresponding to maleic anhydride in the vicinity of 1784 cm ⁻¹ disappears, and the maleic anhydride-modified polypropylene and the polyetheramine are completely bonded. confirmed. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

  To 20 g of the obtained yellow polymer, 80 g of THF was added and completely dissolved at 65 ° C. 100 g of pure water was added dropwise at the same temperature over 1 hour to obtain a hazy yellow solution. This was cooled to 40 ° C., the pressure reduction degree was gradually reduced from 0.03 MPa to 0.0045 MPa, and THF and water were distilled off under reduced pressure until the concentration became 25% by mass, and a translucent pale yellow aqueous resin dispersion was obtained. Got. It seems to be translucent due to the small dispersed particle size.

As a result of measuring the dispersed particle size, the 50% particle size was 0.04 μm, and the 90% particle size was 0.07 μm.
Methoxypoly (oxyethylene / oxypropylene) -2-propylamine (a polyether amine manufactured by Huntsman Corp .; Jeffamine M-1000) has an insoluble content when dissolved in water at 25 ° C. at a concentration of 10% by mass. It is 1 mass% or less and is a hydrophilic polymer.

[Production Example 4: Production of maleic acid-modified polypropylene aqueous dispersion]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 20 g of maleic anhydride-modified polypropylene obtained in Production Example 2 and 80 g of toluene were added and heated to 110 ° C. to be completely dissolved. After cooling to 50 ° C., 5 g of polyoxyethylene cetyl ether (nonionic surfactant, Emulgen 220 manufactured by Kao Corporation, HLB = 14.2) and polyoxyethylene lauryl ether (nonionic surfactant, Kao ( Emulgen 147, HLB = 16.3) 5 g was added and dissolved, and then cooled to 35 ° C.

After 100 g of water was added and sufficiently stirred, emulsification was carried out at 21000 rpm for 3 minutes using an internal shear type emulsifier CLEARMIX CLM-0.8S (manufactured by M Technique). Subsequently, an aqueous solution obtained by diluting 2-amino-2-methyl-1-propanol with water to 10% by mass was added to adjust the pH to 8. The crude emulsion was gradually reduced in pressure from 0.02 MPa to 0.0045 MPa at a temperature of 50 ° C., and toluene and water were distilled off to obtain a milky white resin dispersion having a concentration of 25% by mass.
As a result of measuring the dispersed particle size, the 50% particle size was 0.25 μm, and the 90% particle size was 3.1 μm. Both the 50% particle size and 90% particle size were significantly larger than in the examples.

[Production Example 5: Production of pigment dispersion paste]
A water-soluble acrylic resin (John Crill 683 manufactured by Johnson Polymer Co., Ltd. (resin acid value 160 mgKOH / g)) was neutralized with 2-amino-2-methylpropanol and dissolved in water.
20 g of this aqueous solution (solid content concentration 25%), 7.5 g of carbon black (manufactured by Mitsubishi Chemical), 60 g of titanium oxide (R-5N manufactured by Sakai Chemical Industry Co., Ltd.), antifoaming agent (Surfinol 440 manufactured by Air Products) 2 0.5 g, ion-exchanged water 60 g, and zirconia beads 150 g were mixed and stirred for 30 minutes in a paint shaker to disperse. The dispersion was filtered through a 400 mesh wire mesh to obtain a pigment dispersion paste having a solid content concentration of 50%.

[Production Example 6: Production of propylene-based polymer]
12.9% by mass of propylene-ethylene in the same manner as in Production Example 1 except that the polymerization temperature was 50 ° C., the total pressure during polymerization was 0.5 MPa, and ethylene was introduced in an amount of 6.3% of the total pressure. 11 kg of copolymer toluene solution was obtained (1.42 kg of propylene polymer). The resulting propylene-ethylene copolymer had a weight average molecular weight Mw of 217,000, a stereoregularity [mmmm] of 40.1%, and an ethylene content of 3.1 mol%.

[Production Example 7: Production of maleic anhydride-modified propylene polymer]
A maleic anhydride-modified propylene-ethylene copolymer was obtained in the same manner as in Production Example 2 except that the propylene-ethylene copolymer obtained in Production Example 6 was used. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.3% by mass (0.12 mmol / g). The weight average molecular weight was 116,000.

[Production Example 8: Production of aqueous dispersion of polyalkylene glycol-modified propylene polymer]
Except for using the maleic anhydride-modified propylene-ethylene copolymer of Production Example 7, the same operation as in Production Example 3 was carried out to obtain a translucent light yellow aqueous resin dispersion. It seems to be translucent due to the small dispersed particle size.
As a result of measuring the dispersed particle size, the 50% particle size was 0.016 μm, and the 90% particle size was 0.027 μm.

[Example 1: Aqueous resin dispersion]
Using 12 g of polyalkylene glycol-modified polypropylene aqueous resin dispersion obtained in Production Example 3 as a propylene polymer resin (3 g in terms of solid content), 20 g of Vylonal MD-1200 is blended with 7 g in terms of solid content, An aqueous resin dispersion of propylene polymer / polyester = 30/70 (mass ratio) was obtained. The evaluation results are shown in Table-1.

[Examples 2 and 3, Comparative Examples 1 to 6]
An aqueous resin dispersion was obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used. The evaluation results are shown in Table-1. In the table, the components (C) and (D) are values in terms of solid content.

It can be seen that the aqueous resin dispersions of Examples 1 to 3 are excellent in all of cell properties, initial adhesion, and moisture resistance, and no bleed out is observed.
[Examples 4-6, Comparative Examples 7-9: Paint]
Paints were produced with the formulations shown in Table-2. Butyl cellosolve (ethylene glycol monobutyl ether) is contained as a film-forming aid. The evaluation results are shown in Table-2. In the table, the components (C) and (D) are values in terms of solid content.

It can be seen that the coating materials of Examples 4 to 6 are excellent in all of air bubbles, initial adhesion, moisture resistance, and beef tallow resistance, and no bleed out is observed.
[Production Example 9: Production of polypropylene]
In a 1,000 ml round bottom flask, 110 ml of demineralized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved with stirring. In this solution, 16.7 g of commercially available granulated montmorillonite (Mizusawa Chemical Benclay SL) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The recovered cake was slurried again with 500 ml of demineralized water in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite.

To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To this suspension was added 80 ml of toluene, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In another flask, 0.2 mmol of triisobutylaluminum (manufactured by Tosoh Akzo) was collected, and 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H- 1-Azulenyl) hafnium 131 mg (57 μmol) in toluene was added, and the mixture was stirred at room temperature for 10 minutes to obtain a catalyst slurry (see JP-A 2004-002310 for the method for producing the catalyst).

  Subsequently, 11 L of toluene, 3.5 mmol of triisobutylaluminum and 2.64 L of liquid propylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 67 ° C., and the stirring was continued at the same temperature for 2 hours while keeping the total pressure at the time of polymerization constant at 0.65 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and the clay residue were removed. As a result, 11 kg (1.5 kg propylene polymer) of a 13.5% by mass propylene polymer toluene solution was obtained. The resulting polypropylene had a weight average molecular weight Mw of 191,000 and stereoregularity [mmmm] of 45.8%.

[Production Example 10: Production of maleic anhydride-modified polypropylene]
Into a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 650 g of toluene and 350 g of the polypropylene obtained in Production Example 9 were placed, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After heating, 14 g of maleic anhydride was added, and 4.7 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued by stirring at the same temperature for 10 hours. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a white powdery modified polymer. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.25% by mass (0.125 mmol / g as maleic anhydride groups, -C (= O) O- 0.25 mmol / g) in terms of the group represented by The weight average molecular weight was 120,000.

[Production Example 11: Production of maleic anhydride-modified polypropylene]
The same procedure as in Production Example 2 was carried out except that the amount of maleic anhydride was 28 g and the amount of t-butylperoxyisopropyl monocarbonate was 9.3 g. The maleic anhydride group content (grafting ratio) was 2.4% by mass (0.24 mmol / g as maleic anhydride group, 0.48 mmol / g in terms of —C (═O) O— group). It was. The weight average molecular weight was 100,000.

[Production Example 12: Production of maleic anhydride-modified polypropylene]
The same procedure as in Production Example 2 was conducted except that the amount of maleic anhydride was 21 g and the amount of t-butylperoxyisopropyl monocarbonate was 7.0 g. The maleic anhydride group content (graft ratio) was 1.6% by mass (0.16 mmol / g as maleic anhydride group, 0.32 mmol / g in terms of —C (═O) O— group). It was. The weight average molecular weight was 110,000.

[Production Example 13: Production of maleic anhydride-modified polypropylene]
The same procedure as in Production Example 10 was carried out except that the amount of maleic anhydride was 105 g and the amount of t-butylperoxyisopropyl monocarbonate was 70 g. The maleic anhydride group content (graft ratio) was 5.1% by mass (0.51 mmol / g as maleic anhydride group, 1.02 mmol / g in terms of —C (═O) O— group). It was. The weight average molecular weight was 68,000.

[Production Example 14: Production of polyalkylene glycol-modified polypropylene aqueous dispersion]
In a glass flask equipped with a reflux condenser, thermometer, and stirrer, 30 g of maleic anhydride-modified polypropylene obtained in Production Example 10 (maleic anhydride group content: 3.75 mmol) and 60 g of toluene were added, and the temperature was adjusted to 110 ° C. The temperature was raised and the solution was completely dissolved. Subsequently, 7.5 g (7.5 mmol, propylene-based polymer (A)) of methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000, molecular weight 1000 (nominal value)) A solution of hydrophilic polymer (B) corresponding to 25 parts by mass) in 10 g of toluene was added to 100 parts by mass, and the mixture was reacted at 110 ° C. for 3 hours.

After cooling, toluene was distilled off under reduced pressure to obtain 37 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, the peak corresponding to maleic anhydride near 1784 cm ⁻¹ disappears, and the maleic anhydride-modified polypropylene and the polyetheramine are completely bonded. Observed. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

  75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 84 g of pure water was added dropwise at the same temperature over 1 hour to obtain a hazy yellow solution. This was cooled to 40 ° C., gradually reduced in pressure from 0.03 MPa to 0.0045 MPa, and then distilled off under reduced pressure to a concentration of 25% by mass to obtain a translucent light yellow resin dispersion. It seems to be translucent due to the small dispersed particle size.

As a result of measuring the dispersed particle size, the 50% particle size was 0.068 μm.
The methoxypoly (oxyethylene / oxypropylene) -2-propylamine (polyetheramine manufactured by Huntsman; Jeffamine M-1000) used was insoluble when dissolved in water at 25 ° C. at a concentration of 10% by mass. Is 1% by mass or less and is a hydrophilic polymer.

[Production Example 15: Production of polyalkylene glycol-modified polypropylene aqueous dispersion]
30 g of maleic anhydride-modified polypropylene obtained in Production Example 11 (maleic anhydride group content: 7.2 mmol) was used as maleic anhydride-modified polypropylene, and 14.4 g (14.4 mmol, propylene-based heavy) of Jeffamine M-1000 was used. 44 g of a yellow polymer was obtained in the same manner as in Production Example 14 except that the hydrophilic polymer (B) was used in an amount of 48 parts by mass based on 100 parts by mass of the union (A). A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

80 g of THF was added to 20 g of the obtained yellow polymer and completely dissolved at 60 ° C. 100 g of pure water was added dropwise at the same temperature over 1 hour to obtain a yellow solution. This was cooled to 40 ° C., the pressure reduction degree was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off to a concentration of 20% by mass to obtain a transparent yellow resin dispersion. The dispersed particle size is so fine that it appears to be almost transparent.
The dispersed particle size was measured, and the 50% particle size was 0.011 μm.

[Production Example 16: Production of polyalkylene glycol-modified polypropylene aqueous dispersion]
In a glass flask equipped with a reflux condenser, thermometer, and stirrer, 30 g of maleic anhydride-modified polypropylene obtained in Production Example 12 (maleic anhydride group content: 4.8 mmol) and 70 g of toluene were added, and the temperature was adjusted to 110 ° C. The temperature was raised and it was completely dissolved. Next, 4.5 g (4.5 mmol, equivalent to 15 parts by mass of the hydrophilic polymer (B) per 100 parts by mass of the propylene-based polymer (A)) and a solution obtained by dissolving 4.5 g of toluene in Jeffamine M-1000, The mixture was further reacted at 110 ° C. for 1 hour. Thereafter, 0.4 g (4.5 mmol) of morpholine was added and reacted at 110 ° C. for 1 hour.

After cooling, toluene was distilled off under reduced pressure to obtain 34 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, it was confirmed that 90% of the peak corresponding to maleic anhydride near 1784 cm ⁻¹ disappeared, and maleic anhydride-modified polypropylene and polyetheramine were bonded. Observed. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified polypropylene is formed.

75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 84 g of pure water was added dropwise at the same temperature over 1 hour to obtain a hazy yellow solution. This was cooled to 40 ° C., gradually reduced in pressure from 0.03 MPa to 0.0045 MPa, and then distilled off under reduced pressure to a concentration of 25% by mass to obtain a translucent light yellow resin dispersion. It seems to be translucent due to the small dispersed particle size.
As a result of measuring the dispersed particle size, the 50% particle size was 0.086 μm.

[Production Example 17: Production of polyalkylene glycol-modified polypropylene aqueous dispersion]
Instead of maleic anhydride-modified polypropylene, maleic anhydride-modified chlorinated polypropylene (manufactured by Toyo Kasei Co., Ltd., maleic anhydride group content (graft ratio) is 2.1 mass% (0.21 mmol / g)) is used. 9 g of Min M-1000 (9 mmol, equivalent to 30 parts by mass of the hydrophilic polymer (B) with respect to 100 parts by mass of the propylene-based polymer (A)) Got. A graft copolymer in which polyetheramine is graft-bonded to maleic anhydride-modified chlorinated polypropylene is formed.

75 g of THF was added to 25 g of the obtained yellow polymer and completely dissolved at 60 ° C. 100 g of pure water and 0.9 g (10 mmol) of 2-amino-2-methyl-1-propanol were added dropwise at the same temperature over 1 hour to obtain a yellow solution. This was cooled to 40 ° C., the pressure reduction degree was gradually reduced from 0.03 MPa to 0.0045 MPa, and the pressure was distilled off to a concentration of 20% by mass to obtain a transparent yellow resin dispersion. The dispersed particle size is so fine that it appears to be almost transparent.
As a result of measuring the dispersed particle size, the 50% particle size was 0.072 μm.

[Production Example 18: Production of maleic anhydride-modified polypropylene aqueous dispersion]
75 g of THF was added to 25 g of maleic anhydride-modified polypropylene obtained in Production Example 13 (content of maleic anhydride 12.75 mmol) in a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, and completely dissolved at 60 ° C. . To this solution, 2.3 g (26.0 mmol) of N, N-dimethylethanolamine was added dropwise, and then 84 g of pure water was added dropwise at the same temperature over 1 hour to obtain a dull yellow solution. This was cooled to 40 ° C., gradually reduced in pressure from 0.03 MPa to 0.0045 MPa, and then distilled off under reduced pressure to a concentration of 25% by mass to obtain a translucent light yellow resin dispersion. It seems to be translucent due to the small dispersed particle size.
As a result of measuring the dispersed particle size, the 50% particle size was 0.060 μm.

[Production Example 19: Production of maleic anhydride-modified propylene polymer]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 650 g of toluene, 175 g of polypropylene obtained in Production Example 9, and a propylene-1-butene copolymer produced by a metallocene catalyst (manufactured by Mitsui Chemicals, Inc.) 175 g of Toughmer XM-7070, propylene / 1-butene = 75/25 (molar ratio), weight average molecular weight Mw 240,000, Mw / Mn = 2.2, melting point 80 ° C.), and the inside of the container is replaced with nitrogen gas The temperature was raised to 110 ° C. After heating, 35 g of maleic anhydride was added, 17.5 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, acetone was added in the same manner as in Production Example 2, and the precipitated polymer was filtered to obtain a white powdery maleic anhydride-modified polymer. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 2.0% by mass (0.20 mmol / g as maleic anhydride groups, —C (═O) O— groups. Converted to 0.40 mmol / g).

[Production Example 20: Production of aqueous dispersion of polyalkylene glycol-modified propylene polymer]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 30 g of the maleic anhydride-modified propylene polymer obtained in Production Example 19 and 70 g of toluene were added, and the temperature was raised to 110 ° C. to completely dissolve. Next, 6.0 g of Jeffamine M-1000 (corresponding to 20 parts by mass of the hydrophilic polymer (B) with respect to 100 parts by mass of the propylene polymer (A)) and a solution dissolved in 6.0 g of toluene were added at 110 ° C. The reaction was performed for 3 hours. Here, THF was added dropwise in the same manner as in Production Example 3 and then distilled under reduced pressure to obtain a translucent light yellow aqueous resin dispersion. Because the dispersed particle size is fine, it looks translucent. As a result of measuring the dispersed particle size, the 50% average particle size was 0.009 μm, and the 90% particle size was 0.011 μm.

[Production Example 21: Production of maleic anhydride-modified propylene polymer]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 650 g of toluene, a propylene-1-butene copolymer produced by Ziegler-Natta catalyst (Mitsui Chemicals, Tuffmer XR-110T, propylene / 1-butene = 76/24 (molar ratio), weight average molecular weight Mw 290,000, Mw / Mn = 4.1, melting point 110 ° C.) 350 g was added, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. . After heating, 35 g of maleic anhydride was added, 17.5 g of t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, acetone was added in the same manner as in Production Example 2, and the precipitated polymer was filtered to obtain a white powdery maleic anhydride-modified polymer. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 2.1% by mass (0.21 mmol / g as maleic anhydride groups, —C (═O) O— groups. Converted to 0.42 mmol / g).

[Production Example 22: Production of aqueous dispersion of polyalkylene glycol-modified propylene polymer]
In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 30 g of the maleic anhydride-modified propylene polymer obtained in Production Example 21 and 70 g of toluene were added, and the temperature was raised to 110 ° C. and completely dissolved. Next, 7.5 g of Jeffermin M-1000 (corresponding to 25 parts by mass of the hydrophilic polymer (B) with respect to 100 parts by mass of the propylene polymer (A)) and a solution dissolved in 6.0 g of toluene were added at 110 ° C. The reaction was performed for 3 hours. Here, THF was added dropwise in the same manner as in Production Example 3, and the mixture was distilled off under reduced pressure. The average particle diameter of the obtained emulsion was as large as 1 μm or more, and there were many precipitates, and a good aqueous dispersion could not be obtained.

[Production Example 23: Production of aqueous polypropylene dispersion modified with non-hydrophilic polymer]
To 30 g of maleic anhydride-modified polypropylene obtained in Production Example 10 (content of maleic anhydride group: 3.75 mmol), 7.5 g of polyester polyol (P-2010 manufactured by Kuraray Co., Ltd., molecular weight 2000 (nominal value)) (3 .75 mmol, equivalent to 25 parts by mass with respect to 100 parts by mass of polyolefin (A)), and 37 g of yellow polymer were obtained in the same manner as Example 1 except that 0.3 g of dimethylbenzylamine was added. A graft copolymer is formed by grafting polyester polyol to maleic anhydride-modified polypropylene.

80 g of THF was added to 20 g of the obtained yellow polymer and completely dissolved at 60 ° C. When 100 g of pure water was added dropwise at the same temperature over 1 hour, the yellow polymer was separated and a resin dispersion could not be obtained.
The polyester polyol used (P-2010 manufactured by Kuraray Co., Ltd.) is not a hydrophilic polymer because its insoluble content exceeds 1% by mass when dissolved in water at 25 ° C. at a concentration of 10% by mass.

[Examples 7 to 12, Comparative Examples 10 to 12]
10 g of the resin dispersions (solid content concentration: 25% by mass) of Production Examples 14 to 19 and 10 g of the pigment dispersion paste (solid content concentration: 50% by mass) of Production Example 5 and the aqueous acrylic resin dispersion ES-20 (Central Rika) Rikabond ES-20 manufactured by Kogyo Co., Ltd., solid content concentration: 44%, resin Tg: 47 ° C.) 5.7 g was added and mixed to prepare a paint, and the adhesion, water resistance, and GH resistance were evaluated by the following methods. .
However, in Comparative Examples 11 and 12 (Production Examples 22 and 23), the dispersion state was poor and a coating test could not be performed.
The results are shown in Table-3. It can be seen that the paints of Examples 7 to 12 are excellent in initial adhesion, moisture resistance, and GH resistance.

-Adhesion The board | substrate which made the injection molding of 70 mm x 150 mm x 3 mm the grade of polypropylene for automobile exterior was created, and the substrate surface was wiped with isopropyl alcohol. Here, the resin dispersion liquid whose concentration was adjusted so as to have a solid content of 20% by mass was spray-coated so that the coating amount was about 5 to 10 g / m ² . Next, the coated test piece was dried in a safe ben dryer at 80 ° C. for 10 minutes and then allowed to stand at 25 ° C. for 1 hour. Next, acrylic polyol urethane paint Retan PG80III (manufactured by Kansai Paint Co., Ltd.) as a base coat is blended with a predetermined curing agent, the viscosity is adjusted with a special thinner, and the dry coating amount is 50 to 60 g / m ^2. Was applied by spraying and baked at 80 ° C. for 30 minutes to obtain a coated plate.

  After leaving at 25 ° C. for 24 hours, a test piece with a grid pattern was prepared in accordance with the grid pattern test method described in JIS K 5400, and cellophane tape (Nichiban Co., Ltd.) was applied, It peeled in the direction of 90 degree | times and evaluated by the number of grids which were not peeled among the grids 100. FIG.

-Water resistance The coating board produced similarly to the adhesiveness test was immersed in 40 degreeC warm water for 10 days, and the coating external appearance was determined visually. Further, a cross-cut test was performed, and the cross-cut 100 out of the cross-cut 100 was evaluated by the number of cross-cuts.
・ GH resistance The coated plate prepared in the same manner as in the adhesion test is immersed in a mixture of regular gasoline and ethanol (volume ratio: regular gasoline / ethanol = 9/1) kept at 20 ° C. to prevent peeling. The time to reach 5 mm was measured.

Claims (12)

From particles composed of a polymer (C) containing a propylene polymer (A) and at least one resin (D) selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl ester resin Each of the resulting particles is dispersed in water, and the polymer (C) is converted into a group in which the carboxylic acid derivative group is represented by —C (═O) O— in the propylene-based polymer (A). bound at a rate of 0.01~5mmol / g, it is those polyether resin formed by grafted with an amino group to the carboxylic acid derivative group as a hydrophilic polymer (B), and the following (1) to An aqueous resin dispersion characterized by satisfying (4).
(1) The mass ratio of the propylene polymer (A) to the resin (D) is 90:10 to 10:90. (2) The total amount of the polymer (C) and the resin (D) and the mass of water. The ratio is 5:95 to 60:40 (3) The surfactant content is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer (C) and the resin (D) (4) polymer ( The volume average particle diameter of the particles made of C) is 0.5 μm or less and 0.9 times or less the volume average particle diameter of the particles made of the resin (D).   The polymer (C) is a polymer obtained by bonding the hydrophilic polymer (B) to the propylene polymer (A) at a ratio of (A) :( B) = 100: 5 to 100: 500 (mass ratio). The aqueous resin dispersion according to claim 1, which is a coalescence. The aqueous resin dispersion according to claim 1 or 2 , wherein the propylene-based polymer (A) is a stereoblock polypropylene polymer having an isotactic block and an atactic block. The propylene-based polymer (A) is a stereoblock polypropylene polymer containing an isotactic block and an atactic block, and a carbon atom of a methyl group in a propylene unit chain part consisting of a head-to-tail bond in ¹³ C-NMR. When the chemical shift of the peak top of the peak attributed to the pentad represented by mmmm is set to 21.8 ppm, the peak derived from 19.8 ppm to the total area S of the peak appearing at 22.1 ppm, The ratio of the peak area S ₁ having a peak top of 21.8 ppm (S ₁ / S) is 20% to 70%, and the area of the peak having a peak top of 21.5 to 21.7 ppm (mmmr) when set to S ₂ is _{4 + 2S 1 / S 2>} 5, an aqueous resin dispersion according to any one of claims 1 to 3. The propylene polymer (A) is a propylene-1-butene copolymer, the propylene content is 50 mol% or more and 95 mol% or less, and the molecular weight distribution Mw / Mn of the copolymer (A) is 3.0. The aqueous resin dispersion according to any one of claims 1 to 4 , which has a melting point Tm of 120 ° C or lower. The aqueous resin dispersion according to any one of claims 1 to 5 , wherein the propylene polymer (A) is produced using a metallocene catalyst. Furthermore, pigment (E) is comprised, The mass ratio of the total amount of polymer (C) and resin (D), and pigment (E) is 100: 10-100: 400, Any of Claim 1 thru | or 6 2. The aqueous resin dispersion according to item 1. A carboxylic acid derivative group is bonded to the propylene polymer (A) in a ratio of 0.01 to 5 mmol / g in terms of a group represented by -C (= O) O-, and the carboxylic acid derivative group is hydrophilic. A polymer (C) obtained by graft- bonding a polyether resin having an amino group as the conductive polymer (B) at a ratio of (A) :( B) = 100: 5 to 100: 500 (mass ratio). And a dispersion obtained by dispersing in water at least one resin (D) selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl ester resin. Let me
The mass ratio of the propylene polymer (A) to the resin (D) is 90:10 to 10:90, and the mass ratio of the total amount of the polymer (C) and the resin (D) to water is 5:95. A method for producing an aqueous resin dispersion, wherein the aqueous resin dispersion is ˜60: 40. A paint comprising the aqueous resin dispersion according to any one of claims 1 to 7 . The aqueous resin dispersion according to any one of claims 1 to 7 or the paint according to claim 9 is applied to the thermoplastic resin molded body (F) and heated to form a resin layer. The manufacturing method of a laminated body. At least selected from the group consisting of a polymer (C) containing a propylene polymer (A) and an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl ester resin on the thermoplastic resin molded body (F). One or more resins (D) in a mass ratio of 90:10 to 10:90 of (A) :( D), wherein the polymer (C) has a carboxylic acid derivative group in the propylene-based polymer (A). A polyether having an amino group as a hydrophilic polymer (B) bonded to the group represented by —C (═O) O— at a ratio of 0.01 to 5 mmol / g in terms of a group represented by —C (═O) O— The resin is formed by graft bonding, and has a layer having a surfactant content of 10 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer (C) and the resin (D). , Laminate. A resin layer is formed by applying the aqueous resin dispersion according to any one of claims 1 to 7 or the paint according to claim 9 to the thermoplastic resin molding (F) and heating. The laminated body characterized by the above-mentioned.