JP2011256236A - Coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material which comprises a propylenic elastomer as a main component, contains no chlorine and no organic solvent, and expresses superior adhesiveness to various resin molded bodies comprising polypropylene being a hardly-adhesive plastic, particularly comprising various engineering plastics.SOLUTION: There is provided a coating material produced by blending a water-based resin containing a propylenic elastomer whose melting point is not observed by differential scanning calorimetric analysis (DSC) and another water-based resin containing a propylenic elastomer whose melting point is less than 100°C. The coating material causes no separation phenomenon, can be used as it is, enables a spray coating, and has a nonconventional functional effect such that the material is excellent in adhesiveness to a hardly-adhesive plastic, particularly to various resin molded products comprising polypropylene or various engineering plastics.

Description

  The present invention is a coating material in which the thermoplastic elastomer (A) is a propylene-based elastomer as a main component, and particularly an aqueous resin containing a propylene-based elastomer whose melting point is not observed by differential scanning calorimetry (DSC) and a melting point of less than 100 ° C. This is related to a coating material made by mixing two types of water-based resin with a water-based resin containing a propylene-based elastomer. It is related to a coating material that has excellent adhesion to polypropylene, which is a difficult-to-adhere plastic, especially various engineer plastics. It is.

Engineer plastics have excellent heat resistance, oil resistance, moldability, rigidity, toughness, etc., so power tools, general industrial parts, mechanical parts, electronic parts, automotive interior and exterior parts, engine room parts It is widely used as various functional parts such as automobile electrical parts. However, many of these engineer plastics are very rigid in painting and bonding and have high crystallinity due to their properties, and it is very difficult to perform coating and bonding on general-purpose coating materials. .
For this reason, when applying or bonding engineer plastics, surface adhesion has been improved by activating the surface with chromic acid, flame, corona discharge, plasma, solvent, etc. . For example, a resin composition (Patent Document 1) including a chlorinated modified propylene-based random copolymer, a stabilizer, and an organic solvent has been proposed for coating on a nylon base material. However, these contain chlorine and organic solvents such as toluene and xylene, and there are concerns about safety and environmental pollution.

In addition, polyolefin resins generally have high productivity and excellent moldability, and have many advantages such as light weight, rust prevention, and impact resistance. It is widely used as furniture, miscellaneous goods, building materials, etc. Such polyolefin-based resin molded products are generally non-polar and crystalline, unlike synthetic resins having polarity typified by polyurethane resins, polyamide resins, acrylic resins, and polyester resins. For this reason, it is very difficult to perform coating and adhesion to a general-purpose resin composition.
For this reason, when coating or adhering to a polyolefin resin molded product, the surface adhesion is improved by activating the surface with chromic acid, flame, corona discharge, plasma, solvent, etc. I have been. For example, in automotive bumpers, the surface is etched with a halogen-based organic solvent such as trichloroethane to improve adhesion to the coating film, or after pretreatment such as corona discharge treatment, plasma treatment, or ozone treatment. However, the purpose of painting and bonding has been made. In addition, a method of treating the surface of a substrate such as a molded article with a primer is employed. For example, a composition in which maleic acid is introduced into a polyolefin (Patent Document 2), and a composition containing chlorinated modified polyolefin as a main component are water. (Patent Document 3), olefin polymer dispersed in water (Patent Document 4), and the like have been proposed.

JP 2003-321588 A Japanese Patent Publication No. 62-21027 JP-A-1-256556 WO2007-77843

  An object of the present invention is an improvement of the above-described problems, and does not contain chlorine or an organic solvent, and exhibits excellent adhesion to molded products made of polypropylene, which is a difficult-to-adhere plastic, in particular, various resins made of various engineer plastics. It is providing the coating material which has a propylene-type elastomer as a main component.

  As a result of intensive studies and studies to achieve the above object, the present inventors have found that an aqueous resin containing a propylene-based elastomer whose melting point is not observed by differential scanning calorimetry (DSC) and a melting point of less than 100 ° C. The present inventors have found that a coating material obtained by mixing two types of water-based resins with a water-based resin containing a propylene-based elastomer is extremely effective for achieving the above-mentioned target, and has completed the present invention. That is, [1] to [10] below.

[1] The thermoplastic elastomer (A) is an unmodified thermoplastic elastomer (a-1) and / or a monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group. A thermoplastic elastomer (a-2) modified with a resin (B) and / or a thermoplastic elastomer (a-3) modified with a urethane resin (C),
The thermoplastic elastomer (A1) -containing water-based resin including the unmodified thermoplastic elastomer (a-1-1) satisfying the following (i) to (iii), and the following (i) and (ii) A coating material obtained by mixing two types of water-based resins of thermoplastic elastomer (A2) -containing water-based resin including unmodified thermoplastic elastomer (a-1-2) satisfying (iv).
(I) At least one copolymer of propylene and an α-olefin having 4 to 20 carbon atoms other than propylene, containing 53 mol% or more of propylene, 1 to 47 mol% of α-olefin having 4 to 20 carbon atoms, ethylene A propylene polymer having a content of 0 to 25 mol%.
(Ii) The weight average molecular weight by gel permeation chromatography (GPC) is 50,000 or more and 800,000 or less.
(Iii) No melting point is observed by differential scanning calorimetry (DSC).
(Iv) Melting point measured by differential scanning calorimetry (DSC) is less than 100 ° C.
[2] The coating material according to [1], wherein the water-based resin containing the thermoplastic elastomer (A1) further contains isotactic polypropylene (a-4).
[3] The solid content of the water-based resin containing the thermoplastic elastomer (A1) is 70 to 99% by weight of the total of (a-1), (a-2), and (a-3), isotactic. The coating material according to [2], wherein polypropylene (a-4) is 1 to 30% by weight.
[4] The monomer (b-1) having an α, β-monoethylenically unsaturated group of (a-2) is at least one active hydrogen group selected from a hydroxyl group, a carboxyl group, and an amino group. The coating material according to [1].
[5] An aqueous resin and / or a urethane resin comprising an aqueous resin containing the thermoplastic elastomer (A) according to [1] and a resin (B) comprising a monomer having an α, β-monoethylenically unsaturated group ( A coating material comprising a mixture of a water-based resin (C) and a water-based resin of petroleum-based hydrocarbon resin (D) and / or rosin-based resin (E) and / or terpene-based resin (F).
[6] 1 to 90 parts by weight of the resin (B) and / or the resin (C) with respect to 100 parts by weight of the solid content of the water-based resin containing the thermoplastic elastomer (A) according to [1], The coating material according to [5], wherein the resin (D) and / or the resin (E) and / or the resin (F) are mixed so as to be 1 to 95 parts by weight.
[7] The water-based resin containing the thermoplastic elastomer (A) according to [1] is an unmodified thermoplastic elastomer (a-1) and / or a monomer having an α, β-monoethylenically unsaturated group ( b-1) or the thermoplastic elastomer (a-2) modified with the resin (B) comprising (b-1) and the group of carboxylic acid or its salt bonded to the polymer chain is represented by the formula (1 -C-O-
・ ・ ・ (1)
O
A group of propylene-based resin (a-5) and / or a higher fatty acid or a salt thereof (a-6) which is contained at a concentration of 0.05 to 5 mmol equivalent in terms of the group represented by the formula (a-2) The coating according to any one of [1] to [6], wherein when is a propylene-based resin containing a carboxylic acid or a salt thereof, the weight average molecular weight is larger than that of (a-5). Wood.
[8] The thermoplastic elastomer (A) is a total of 100 parts by weight of the (a-1) and (a-2), and the (a-5) and / or (a-6) is 0.3 to The coating material according to [7], which is 100 parts by weight.
[9] The coating material according to [7] or [8], wherein the aqueous resin containing the thermoplastic elastomer (A) according to [1] further contains an anionic and / or nonionic surfactant (H).
[10] The thermoplastic elastomer (A) is 0.3 to 40 parts by weight based on 100 parts by weight of the total of (a-1) and (a-2). The coating material described.

  The coating material of the present invention can be used as it is without causing a separation phenomenon, can be spray-coated, and is excellent in adhesion to various resin molded products of difficult-to-adhere plastics, especially polypropylene and various engineer plastics. It has an effect that is not present.

    The coating material of the present invention includes those obtained by dissolving or dispersing the following resins (A) to (F) in water.

[Thermoplastic elastomer (A)]
The thermoplastic elastomer (A) used in the present invention includes the following (a-1) to (a-6).

Unmodified thermoplastic elastomer (a-1)
Examples of the unmodified thermoplastic elastomer (a-1) include those other than propylene and propylene, such as 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1 Examples thereof include α-olefins having 4 to 20 carbon atoms such as heptene, 1-hexene, 1-octene, 1-decene and 1-dodecene, and at least one copolymer of ethylene. The present invention relates to an unmodified thermoplastic elastomer (a-1-1) in which (a-1) satisfies the following (i) to (iii), and (a-1) in the following (i) and (iii): , (Iv) satisfying unmodified thermoplastic elastomer (a-1-2). Here, the thermoplastic elastomer (A) containing (a-1-1) is (A1), and the thermoplastic elastomer (A) containing (a-1-2) is (A2).

(I) Propylene is contained in an amount of 53 mol% or more, an α-olefin having 4 to 20 carbon atoms is preferably 1 to 47 mol%, and an ethylene content is preferably 0 to 25 mol%. In particular, for propylene components, α-olefin components, and ethylene components, propylene components are contained in amounts of 53 to 98 mol%, α-olefin components of 1 to 47 mol%, and ethylene components of 1 to 25 mol%. .Alpha.-olefin / ethylene copolymer is preferable, propylene component is 57 to 90 mol%, α-olefin component is 3 to 35 mol%, and ethylene component is preferably 2 to 20 mol%. It is more preferable to contain an amount of 8 to 30 mol% of the α-olefin component and 5 to 15 mol% of the ethylene component. (Here, the total of the single component derived from propylene, the structural unit derived from ethylene, and the structural unit derived from the α-olefin component is 100 mol%.) Among the α-olefins, butene, 1-octene is preferred.
(Ii) The weight average molecular weight measured by GPC is preferably from 50,000 to 800,000, more preferably from 60,000 to 600,000, still more preferably from 70,000 to 500,000, and the molecular weight distribution ( Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) is preferably 4.0 or less, more preferably 3.0 or less, further preferably 2.5 or less, and a metallocene compound. However, the present invention is not limited to this.
(Iii) The melting point is not observed by differential scanning calorimetry (DSC). If the melting point is not observed, a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in the range of −150 to 200 ° C. That means. The measurement conditions are as described in the examples.
(Iv) The melting point measured by differential scanning calorimetry (DSC) is less than 100 ° C. The measurement conditions are as described in the examples.

  The propylene / α-olefin / ethylene copolymer containing a propylene-derived structural unit, an α-olefin structural unit having 4 to 20 carbon atoms, and, if necessary, an ethylene-derived structural unit in an amount such as (i), The compatibility with the following isotactic polypropylene (a-4) becomes good, and the resulting propylene polymer composition tends to exhibit sufficient transparency, flexibility, heat resistance, and scratch resistance.

The degree of crystallinity measured by X-ray diffraction is usually 0% in the case of (a-1-1), and is usually from 1% to 50% in the case of (a-1-2).
The propylene / ethylene / α-olefin copolymer has a single glass transition temperature, and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually −10 ° C. or lower, preferably −15 ° C. It is desirable to be in the following range. When the glass transition temperature Tg of the propylene / α-olefin / ethylene copolymer is within the above range, the cold resistance and the low temperature characteristics are excellent.

The propylene / α-olefin / ethylene copolymer preferably has a triad tacticity (mm fraction) measured by ¹³ C-NMR of 85% or more, more preferably 85 to 97.5% or less, and still more preferably. It is in the range of 87 to 97%, particularly preferably 90 to 97%. When the triad tacticity (mm fraction) is in this range, the balance between flexibility and mechanical strength is particularly excellent, which is suitable for the present invention. The mm fraction can be measured by the method described in International Publication No. 2004-087775 pamphlet, page 21, line 7 to page 26, line 6.

Thermoplastic elastomer (a-2) modified with resin (B) comprising monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group
Thermoplastic elastomer (a-2) modified with resin (B) comprising monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group used in the present invention Is a resin comprising the monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group described below in the unmodified thermoplastic elastomer (a-1) described above. Although it is obtained by modifying in (B), there is no problem even if some of them do not react.

As the monomer (b-1) having an α, β-monoethylenically unsaturated group used in the present invention, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (Meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzine (Meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. (Meth) acrylic acid esters, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy- Hydroxyl group-containing vinyls such as 3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate Carboxyl group-containing vinyls such as monohydroxyethyl acrylate and phthalic acid, and monoesters thereof, amides such as chloramide, N-methylol acrylamide, diacetone acrylamide and maleic amide, vinyl such as vinyl acetate and vinyl propionate Esters, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, aminoalkyl (meth) acrylates such as N, N-dihydroxyethylaminoethyl (meth) acrylate, styrene sulfonic acid, styrene sulfonic acid soda, 2-acrylic Unsaturated sulfonic acids such as amido-2-methylpropane sulfonic acid, mono (2-methacryloyloxyethyl) acid phosphate, unsaturated phosphoric acid such as mono (2-acryloyloxyethyl) acid phosphate, other acrylonitrile, methacrylonitrile 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) Acrylate, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like. Moreover, the macromonomer etc. which have the said monomer or its copolymer in a segment, and have a vinyl group at the terminal can also be used. Further, carboxylic anhydrides such as maleic anhydride and citraconic anhydride can also be used.
Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate.

The monomer (b-1) having an α, β-monoethylenically unsaturated group used in the present invention may be one kind or a mixture of plural kinds.
As the resin (B) comprising the monomer (b-1) having an α, β-monoethylenically unsaturated group, the monomer (b-1) having the α, β-monoethylenically unsaturated group is used. It is the polymer which consists of. The amount of the monomer (b-1) having an α, β-monoethylenically unsaturated group is usually 0.1 to 70% by weight of the weight of the unmodified thermoplastic elastomer (a-1), preferably It is 0.3-50 weight%, More preferably, it is the range of 0.5-30 weight%.
The thermoplastic elastomer (a-2) modified with the resin (B) comprising the monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group can be obtained by various methods. For example, a method of removing the solvent after reacting the unmodified thermoplastic elastomer (a-1) and the monomer (b-1) in the presence of the polymerization initiator (G) in an organic solvent, A method of reacting the monomer (b-1) and the polymerization initiator (G) with stirring to a melt obtained by heating and melting the unmodified thermoplastic elastomer (a-1), or an unmodified thermoplastic elastomer A method in which a mixture of (a-1), monomer (b-1) and polymerization initiator (G) is supplied to an extruder and reacted while heating and kneading, or a monomer (b -1) in the presence of a polymerization initiator (G-1), and then the solvent (b) obtained by removing the solvent -1), a resin (B), an unmodified thermoplastic elastomer (a-1), and a polymerization initiator (G) are mixed and supplied to an extruder and reacted while heating and kneading. .

  Examples of the organic solvent that can be used here include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane, decane, isooctane, and isodecane, cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane. Alicyclic hydrocarbons, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ester solvents such as 3 methoxybutyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, etc. These organic solvents can be used, and a mixture of two or more of these may be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferably used.

  As the polymerization initiator (G-1) used in the present invention, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di ( Peroxybenzoate) hexyne-3,1,4-bis (tert-butylperoxyisopropyl) benzene, and the like. These can be used alone or in admixture of two or more.

Thermoplastic elastomer (a-3) modified with urethane resin (C)
The thermoplastic elastomer (a-3) modified with the urethane resin (C) of the present invention is not particularly limited. For example, in an organic solvent, the unmodified thermoplastic elastomer (a-1) and urethane are used. There is a method of mixing the resin (C) and generating a radical at a high temperature and / or a high temperature to carry out the reaction.

In the present invention, the radical generating method in the case of carrying out the reaction by generating a radical is not particularly limited, but a known method such as a method of adding an organic peroxide can be used.
Examples of the organic peroxide include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dicumylperper having a tert-butyl group and / or a benzyl group in the molecule. Examples thereof include oxide, tert-butyl peroxybenzoate, lauroyl peroxide, cumene hydroperoxide and the like. These can be used alone or in admixture of two or more.
In the present invention, among the above-mentioned organic peroxides, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are more preferably used. That is, an organic peroxide having a tert-butyl group and / or a benzyl group in the molecule has a relatively high hydrogen abstraction ability, and has an effect of improving the graft ratio with polyolefin.

  The amount of the organic peroxide used is the unmodified thermoplastic elastomer (a-1) and / or the monomer (b-1) having an α, β-monoethylenically unsaturated group or (b- The range is usually 2 to 50% by weight, more preferably 3 to 30% by weight, based on the total weight of the thermoplastic elastomer (a-2) modified with the resin (B) comprising 1) and the urethane resin (C). Using it in a great effect on stability appears. In this case, when the amount of the organic peroxide used is less than 2% by weight, the resulting composition is poorly stable in the solvent. Since the adhesiveness to the material due to gelation or molecular weight reduction is inferior, it is preferable to use an organic peroxide within the above range. Moreover, it is preferable to add this organic peroxide little by little as much as possible. That is, depending on the amount used, in general, when the organic peroxide is added all at once, the reaction solution is relatively easily gelled. It is preferable to add in small portions separately.

Furthermore, the thermoplastic elastomer (a-3) modified with the urethane resin of the present invention is a resin comprising a monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group ( A product obtained by reacting the functional group of the thermoplastic elastomer (a-2) modified in B) with the functional group of the urethane resin (C) may be used. The thermoplastic elastomer (a-3) modified with a urethane resin is not particularly limited. For example, (a-2) contains a carboxyl group, and (C) has a hydroxyl group or an isocyanate group at the terminal. A method of mixing and containing a reaction under heating, a method of containing a hydroxyl group in (a-2), mixing a compound containing an isocyanate group at the end of (C), and reacting under heating; a-2) contains an acid anhydride group, and this is reacted with an alcohol or resin containing two or more hydroxyl groups in the molecule to contain a hydroxyl group, and then an isocyanate group is added to the terminal of (C). There are various methods, such as a method of mixing a mixture containing a resin and reacting under heating, a method of reacting a thermoplastic elastomer (a-2) having an active hydrogen group with a polyfunctional isocyanate compound, and the above-mentioned method. In the presence of (a-2) containing a xyl group or a hydroxyl group, there is a method of reacting the raw material monomer of (C) to synthesize a urethane resin and modifying the latter, the latter being from the viewpoint of storage stability preferable.
From the viewpoint of water dispersibility and adhesion to the substrate, the unmodified thermoplastic elastomer (a-1) and / or monomer having an α, β-monoethylenically unsaturated group (b- The ratio of the thermoplastic elastomer (a-2) modified with the resin (B) consisting of 1) or (b-1) and the urethane resin (C) is (a-1) and / or (a-2) / (C) = weight ratio of 10/90 to 95/5, preferably 20/80 to 80/20.

Isotactic polypropylene (a-4)
The isotactic polypropylene (a-4) used in the present invention is a polypropylene having an isotactic pentad fraction measured by NMR method of 0.9 or more, preferably 0.95 or more.
The isotactic pentad fraction (mmmm) is measured and calculated by the method described in Japanese Patent Application Laid-Open No. 2003-147135.

Examples of the isotactic polypropylene (a-4) include a propylene homopolymer or a copolymer of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like, and ethylene or α-olefin having 4 to 10 carbon atoms is preferable.
These α-olefins may form a random copolymer with propylene or a block copolymer. The structural unit derived from these α-olefins may be contained in the polypropylene in a proportion of 35 mol% or less, preferably 30 mol% or less.

  Isotactic polypropylene (a-4) has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D 1238 at 0.01 to 1000 g / 10 min, preferably 0.05. It is desirable to be in the range of ˜100 g / 10 minutes.

Further, a plurality of isotactic polypropylenes (a-4) can be used in combination as necessary, and for example, two or more kinds of components having different melting points and rigidity can be used.
Further, as isotactic polypropylene (a-4), homopolypropylene having excellent heat resistance (generally known copolymer having 3 mol% or less copolymer component other than propylene), block polypropylene having excellent balance between heat resistance and flexibility ( Random polypropylene (generally having a normal decane-eluting rubber component of 3 to 30 wt%) and random polypropylene excellent in the balance between flexibility and transparency (generally having a melting point of 110 ° C. to 150 ° C. as measured by DSC) Can be selected or used in combination in order to obtain the desired physical properties.

Such isotactic polypropylene (a-4) is, for example, a Ziegler catalyst system comprising a solid catalyst component, an organoaluminum compound and an electron donor containing magnesium, titanium, halogen and an electron donor as essential components, or a metallocene compound. It can be produced by polymerizing propylene or copolymerizing propylene and another α-olefin in a metallocene catalyst system using as a component of the catalyst.
The content of the component (a-4) is preferably 1 to 30% by weight, more preferably 2 to 27% by weight, and further preferably 2 to 25% by weight in the thermoplastic elastomer (A).

Propylene-based resin (a-5) containing a group of carboxylic acid or a salt thereof bonded to a polymer chain
As the propylene-based resin (a-5) containing a carboxylic acid or salt group bonded to a polymer chain, the carboxylic acid or salt group bonded to the polymer chain is represented by the formula (1) − per gram of resin. C-O-
・ ・ ・ (1)
O
And a propylene-based resin contained at a concentration of 0.05 to 5 mmol equivalent in terms of a group represented by Carboxylic acid salt groups (including partially neutralized or partially saponified carboxylic acid groups) bonded to the polymer chain of the propylene-based resin are 0.05 to as COO groups per gram of the resin. 5 mmol, preferably 0.1-4 mmol.
The propylene resin (a-5) is, for example, an acid-modified propylene resin, a monomer having a neutralized or non-neutralized carboxylic acid group, and / or saponified or saponified. A monomer having an unreacted carboxylic acid ester can be obtained by graft copolymerization.

When (a-2) is a propylene-based resin containing a carboxylic acid or a salt thereof, the weight average molecular weight is larger than that of (a-5).
The molecular weight of the propylene-based resin (a-5) is a weight average molecular weight (hereinafter abbreviated as Mw) measured by GPC. The weight average molecular weight is obtained by, for example, gel permeation chromatography (GPC). Can be measured as a standard.) Is an acid-modified propylene in the range of 1,000 to 50,000, preferably 2,000 to 45,000, more preferably 3,000 to 40,000. Based resins are preferred.

Examples of the monomer having a neutralized or non-neutralized carboxylic acid group and the monomer having a saponified or non-saponified carboxylic acid ester group include, for example, ethylenically unsaturated carboxylic acid , Anhydrides thereof or esters thereof.
Examples of the ethylenically unsaturated carboxylic acid (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic ^TM (Endoshisu as its anhydride -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, and the like, as unsaturated carboxylic acid ester, methyl of the above ethylenically unsaturated carboxylic acid, Examples include monoesters or diesters such as ethyl or propyl. These monomers can be used alone or in combination.

  In order to produce a modified product by graft copolymerization of a graft monomer selected from the above monomers with a grafted polymer, various conventionally known methods can be employed. Examples thereof include a method of melting a grafted polymer and adding a graft monomer and graft copolymerizing, or a method of dissolving in an organic solvent and adding a graft monomer and graft copolymerizing. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a polymerization initiator (G).

The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The ratio of the polymerization initiator used is usually in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the grafted polymer. Among the polymerization initiators (G), dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- Dialkyl peroxides such as (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
Basic materials used for neutralization and saponification include alkali metals such as sodium and potassium, inorganic amines such as hydroxylamine and ammonium hydroxide, methylamine, ethylamine, propylamine, butylamine, benzylamine, triethylamine, mono Ethanolamine, diethylamine, diethanolamine, trimethylamine, triethylamine, triisopropylamine, dimethylethanolamine, triethanolamine, methyldiethanolamine, diethylenetriamine, ethylaminoethylamine, 2-amino-2-methyl-1-propanol, 3-amino-1- Organic amines such as propanol, 1-amino-2-propanol, 2-amino-1-butanol, morpholine, sodium oxide, sodium peroxide, alkali Mention may be made of metal and alkaline earth metal oxides, hydroxides, hydrides, sodium carbonate, and other alkali metal and alkaline earth metal weak acid salts. Monoethanolamine, diethanolamine, dimethylethanolamine, triethanolamine, methyldiethanolamine, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino- 1-butanol and morpholine are preferred.

Group of higher fatty acid or salt thereof (a-6)
As the higher fatty acid or group (a-6) of the salt thereof used in the present invention, a salt of a higher fatty acid having 12 to 60 carbon atoms is preferred, more preferably an alkali metal salt of a higher fatty acid having 15 to 40 carbon atoms, Examples include alkaline earth metal salts and amine salts, and alkali metal salts of montanic acid and oleic acid are preferable.
Further, the salt of the higher fatty acid (a-6) may contain a higher fatty acid and / or an ester of the higher fatty acid in addition to the salt of the higher fatty acid. The alcohol residue constituting the ester preferably has 2 to 30 carbon atoms, and particularly preferably 6 to 20 carbon atoms. Residues can be linear or branched. A mixture of different carbon numbers may be used. Specific examples of the alcohol residue include residues of higher alcohols such as cetyl alcohol, stearyl alcohol, and oleyl alcohol. Montanic acid ester wax and montan wax are particularly suitable.
The salt of the higher fatty acid (a-6) can be obtained by neutralizing the higher fatty acid and / or saponifying the higher fatty acid ester. In this case, it may be a partially neutralized product or a partially saponified product in which a higher fatty acid or a higher fatty acid ester not neutralized or saponified coexists. Examples of the basic substance that can be used for neutralization and saponification are the same as those exemplified for the salt of the propylene-based resin (a-5).

The amount of the propylene resin (a-5) and / or higher fatty acid or salt group (a-6) containing a carboxylic acid or salt group bonded to the polymer chain is the above (a-1). And (a-5) and / or (a-6) is preferably 0.3 to 100 parts by weight, more preferably 1 to 90 parts by weight, with respect to 100 parts by weight in total of (a-2). -60 parts by weight is more preferred.
Here, the mixing ratio of the water-based resin containing the thermoplastic elastomer (A1) and the water-based resin containing the thermoplastic elastomer (a2) is a solid content weight ratio from the viewpoint of adhesion and adhesion to various substrates ( A1) / A2) is preferably 10/90 to 90/10, and is 50/50 to 90/10, more preferably 60/40 to 85/15 when the substrate is engineer plastic.

[Anionic and / or nonionic surfactant (H)]
As the anionic and / or nonionic surfactant (H) used in the present invention, known ones are used without limitation.

Known anionic surfactants can be used. For example, primary higher fatty acid salts, secondary higher fatty acid salts, primary higher alcohol sulfates, and secondary higher alcohol sulfates. Salt, primary higher alkyl sulfonate, secondary higher alkyl sulfonate, higher alkyl disulfonate, sulfonated higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid sulfate sulfonate salt, higher alcohol ether Examples include sulfuric acid sulfonates, higher alcohol ether sulfonates, higher fatty acid amide alkylol sulfates, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, and alkylbenzimidazole sulfonates. .
Among these anionic surfactants, particularly preferred are higher fatty acid salts, particularly alkali metal salts of saturated or unsaturated higher fatty acids having 10 to 20 carbon atoms, such as capric acid, Unsaturated fatty acids such as undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, etc. Mention may be made of alkali metal salts of fatty acids or mixtures thereof.

  As the nonionic surfactant, known ones can be used. For example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid Examples include esters, polyoxyethylene polyhydric alcohol fatty acid esters, fatty acid sucrose esters, alkylolamides, polyoxyalkylene block copolymers, and the like.

As the surfactant, an anionic surfactant and a nonionic surfactant can be used alone, or a plurality of surfactants can be used in combination.
The amount of the surfactant (H) used is preferably about 0.3 to 40% by weight, based on the total of 100 parts by weight of (a-1) and (a-2), and 0.5 to 30% by weight. % Is more preferable, and 0.8 to 20% by weight is particularly preferable.

[Dispersion method in water]
Resin (B) comprising the unmodified thermoplastic elastomer (a-1) obtained above and / or the monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group The method of dispersing the thermoplastic elastomer (a-2) modified in (3) in water is not particularly limited, but for example, a propylene-based polymer containing a carboxylic acid or a salt group bonded to a polymer chain. Using resin (a-5) and / or higher fatty acid (a-6), it can be dispersed in water by the following method. An anionic and / or nonionic surfactant (H) can also be used in order to improve the dispersion stability in water.
The aqueous resin as described above is prepared by melting and kneading the (a-1) and / or the (a-2) and the (a-5) and / or the (a-6). After adding the active substance and water, the mixture is further melt-kneaded, neutralized and / or saponified, and the dispersion (phase inversion) of (a-1) and / or (a-2) in the aqueous phase is performed. After performing melt kneading of (a-1) and / or (a-2), (a-5) and / or (a-6), and (H) After adding a basic substance and water to the mixture, it is further melt-kneaded, neutralized and / or saponified, and dispersed in the aqueous phase of (a-1) and / or (a-2) (phase inversion) ), Or by adding water as a basic substance to (a-5) and / or (a-6) in advance to neutralize and / or saponify this, and (a-1) And / or After melt-kneading with (a-2), water is further added, and melt-kneading is performed to disperse the above-mentioned (a-1) and / or (a-2) in the aqueous phase (phase inversion). It is preferable to manufacture by the method of performing.

The former method is preferred because it is simple and a uniform particle size can be obtained. The melt kneading means used for phase inversion may be any known means, but preferably a kneader, a Banbury mixer, or a multi-screw extruder can be exemplified.
The proportion of the basic substance added for neutralization or saponification is 60 to 250%, preferably 70 to 200% of the total carboxylic acid or carboxylic acid ester.
Further, the aqueous resin obtained by melt kneading and phase inversion preferably contains 1 to 25% of water, and more preferably 1 to 20%. When the water content is less than 1% by weight, phase inversion (resin solid content is changed from a continuous phase to a dispersed phase by water) hardly occurs, and a suitable aqueous resin cannot be obtained. On the other hand, if it exceeds 25% by weight, the aqueous resin has fluidity.
This water-based resin can be used as it is, but it can be replenished with water to reduce the viscosity.

  The thermoplastic elastomer (a-2) modified with the resin (B) comprising the monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group obtained above, And / or the method of dispersing the thermoplastic elastomer (a-3) modified with a urethane resin in water is not particularly limited. For example, the organic solvent may be the above (a-2), and / or A method in which the organic solvent is removed by adding a basic substance and ion-exchanged water to the one in which the (a-3) is dissolved under stirring, or an organic solvent after forced emulsification in ion-exchanged water containing a surfactant. It can be produced by a known method such as a method for removing water or a method for removing an organic solvent after forced emulsification by adding ion-exchanged water containing a basic substance and a surfactant.

[Aqueous resin of resin (B) comprising monomer having α, β-monoethylenically unsaturated group]
(B-1) is mentioned as a monomer which comprises resin (B) which consists of a monomer which has the (alpha), (beta) -monoethylenically unsaturated group used for this invention.
As the monomer (b-1) having an α, β-monoethylenically unsaturated group used in the present invention, a mixture of a plurality of types is usually used.
The aqueous resin of the resin (B) comprising the monomer (b-1) having an α, β-monoethylenically unsaturated group can be obtained by various methods. For example, the monomer in an organic solvent To the resin solution obtained by solution polymerization of (b-1) in the presence of the polymerization initiator (G), after adding a basic substance and ion-exchanged water, a method of removing the organic solvent, or a surfactant It can be produced by a known method such as an emulsion polymerization method in which the monomer (b-1) is polymerized in the presence of a polymerization initiator (G) in the ion-exchanged water contained.
In the former case, it is necessary to contain an acidic group that can be neutralized with a basic substance in (b-1). Specifically, the carboxyl group-containing vinyl described in the above (b-1) is used, and the resin is synthesized with an acid value of 10 mgKOH / g or more. The acid value of the resin is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more. When the acid value is less than 10 mgKOH / g, the hydrophilicity becomes low and it becomes difficult to make it water-based. The acid value described above is a value in a resin (solid) excluding a solvent.

Furthermore, the organic solvent to be used will not be specifically limited if a boiling point is 100 degrees C or less, These solvents can be used individually or in a 2 or more types of mixed state. Use of a solvent having a boiling point exceeding 100 ° C., that is, exceeding the boiling point of water, makes it difficult to completely distill off only the solvent from the solution after forming the aqueous resin, and the high boiling point solvent remains in the film. Affects physical properties. When it is unavoidably used because of performance, it is preferably used in an amount of 10 parts by weight or less based on 100 parts by weight of the aqueous resin of the resin (B) comprising the monomer (b-1).
As the polymerization initiator used for synthesizing the aqueous resin of the resin (B) comprising the monomer (b-1) of the present invention, the polymerization initiator (G) described above can be used. Can be used alone or in combination of two or more.

  The basic substance used for synthesizing the aqueous resin of the resin (B) composed of the monomer (b-1) of the present invention can be the above basic substance, and the addition amount is 50 of the carboxyl group. Neutralize at ~ 100 mol%. Two or more of these may be used in combination.

Examples of the polymerization initiator (G) used in the latter method include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, hydrogen peroxide, the polymerization initiator (G-1) described above, and these. Examples thereof include redox initiators in combination with metal ions such as iron ions and sodium sulfoxylate, formaldehyde, sodium pyrosulfite, sodium hydrogen sulfite, L-ascorbic acid, Rongalite, etc., one or two of these More than one type can be used. The amount of initiator used is usually 0.1 to 5% by weight based on the total amount of monomers. Furthermore, in order to improve the stability to water, said surfactant can be used.
As the aqueous resin of the resin (B) comprising the monomer (b-1) used in the present invention, Tg measured by DSC is preferably -60 ° C to 50 ° C, more preferably -30 ° C to 30 ° C. It is. Moreover, the weight average molecular weight by GPC is preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000.

[Aqueous resin of urethane resin (C)]
Examples of the polyfunctional isocyanate compound that is a component constituting the aqueous resin of the urethane resin (C) used in the present invention include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and octamethylene diisocyanate. Aliphatic polyisocyanates such as various aliphatic polyisocyanates, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexylmethane-diisocyanate, phenylene diisocyanate, tolylene diisocyanate, 4,4′-diisocyanate, etc. Aromatic polyisocyanates, sulfur-containing aliphatic isocyanates such as thiodiethyl diisocyanate, diphenyl sulfide-2,4'-diisocyanate Aromatic sulfide type isocyanates such as diphenyl disulfide-4,4'-diisocyanate, aliphatic disulfide type isocyanates such as diphenylsulfone-4,4'-diisocyanate, and the like, 4-methyl-3- Isocyanatobenzenesulfonyl-4'-isocyanatophenol ester and other sulfonate ester isocyanates, 4,4'-dimethylbenzenesulfonyl-ethylenediamine-4,4'-diisocyanate and other aromatic sulfonic acid amide isocyanates, thiophene And sulfur-containing heterocyclic compounds such as -2,5-diisocyanate.

In addition, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, burette-modified products, dimerization or trimerization reaction products are also used. However, polyfunctional isocyanate compounds other than the above compounds may be used. Moreover, these polyfunctional isocyanate compounds can also be used by 1 type, or 2 or more types of mixtures.
Of the above compounds, the obtained resin, and the yellowing resistance, thermal stability, and light stability of the film after coating it to form a film, or the availability of a polyfunctional isocyanate compound From these, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferred, among which hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,5-bisisocyanatomethylnorbornane, 2,6-bis. Isocyanatomethylnorbornane and derivatives thereof are particularly preferred.

Examples of the active hydrogen compound having at least two active hydrogen groups capable of reacting with the polyfunctional isocyanate compound per molecule include the following. Various polyol compounds: aliphatic polyols such as ethylene glycol, propylene glycol, pentaerythritol and sorbitol, aromatic polyols such as dihydroxynaphthalene and trihydroxynaphthalene, halogenated polyols such as dibromoneopentyl glycol, polyester polyol, polyethylene glycol , Polyether polyols, polythioether polyols, condensation products of organic acids such as oxalic acid and adipic acid and the polyols, addition reaction products of the polyols with alkylene oxides such as ethylene oxide and propylene oxide, alkylene Addition reaction product of polyamine and alkylene oxide, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, caprolactone modified product, 2- Mercaptoethanol, 3-mercapto-1,2-propanediol, and the like.
In addition, polyamino compounds such as ethylenediamine and diethylenetriamine, and α-amino acids such as serine, lysine and histidine can also be used.

In the present invention, the active hydrogen compound is preferably a straight-chain compound having no branched skeleton, and further, a polyester polyol, polyether polyol, polycarbonate polyol having a melting point (Tm) of 40 ° C. or lower, It is preferable to use 50 parts by weight or more and 98 parts by weight or less of polycaprolactone polyol, polyolefin polyol and copolymers or mixtures thereof in 100 parts by weight of all active hydrogen compounds. If it is less than 50 parts by weight, the texture of the film obtained from the aqueous coating material tends to deteriorate, and if it exceeds 98 parts by weight, the film strength and hardness tend to decrease. These compounds may be used alone or in combination of two or more.
In addition, in order to stabilize the water-based resin of the urethane resin (C) used in the present invention, known materials and stabilization techniques can be used, but one kind of carboxyl group, sulfonyl group and ethylene oxide group is used in the molecule. It preferably has at least one, and more preferably has at least one carboxyl group and / or sulfonyl group.

Examples of constituents for introducing these atomic groups include 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, 3,4- Examples include, but are not limited to, diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, polyethylene glycol, polyaddition product of ethylene oxide and propylene oxide, and a polymer of ethylene glycol and the active hydrogen compound. It is not something. By introducing these atomic groups into the molecule, the mechanical stability of the resin and the miscibility with other components tend to be improved.
The preferred amount when using the carboxyl group and / or sulfonyl group-containing compound is such that the acid value in terms of solid content of the urethane resin aqueous resin composition is in the range of 2 to 15 KOHmg / g, more preferably 3 to 12 KOHmg / g. Is within. If the acid value is less than the above range, the mechanical stability of the resin tends to be high.

  The method for producing the urethane resin (C) aqueous resin is not particularly limited, but examples thereof include the following methods. For example, a polyfunctional isocyanate compound, a compound having an active hydrogen group capable of reacting with an isocyanate group in the active hydrogen compound, an active hydrogen group capable of reacting with an isocyanate group in the compound, and a carboxyl in the molecule At least one compound having a group, sulfonyl group or ethylene oxide group is reacted in an equivalent ratio such that an excess of isocyanate groups is present in the presence or absence of a suitable organic solvent to have an isocyanate group at the molecular end. After that, those having a carboxyl group and / or a sulfonyl group in the prepolymer are neutralized with a neutralizing agent such as a tertiary amine, and then this neutralized prepolymer is chain-extended. If an organic solvent is contained in the system after it has been reacted in an aqueous solution containing an agent, remove it. A method that can be removed, a method in which an unneutralized urethane prepolymer obtained by the above method is introduced into an aqueous solution containing a neutralizer and a chain extender, and reacted, or the above method In the neutralized urethane prepolymer obtained in step 1, an aqueous solution having a chain extender is added and reacted, and the neutralized urethane prepolymer obtained by the above method contains a neutralizer. And an aqueous solution having a chain extender is added and reacted to obtain an aqueous dispersion.

The neutralizing agent used in the present invention is not particularly limited, but alkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine, N-methylmorpholine, and N-ethyl. Tertiary amines such as morpholine, pyridine, N-methylimidazole, ammonia, trimethylamine, triethylamine, alkali metals such as lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide Examples of the compound include quaternary ammonium compounds such as tetramethylammonium hydroxide, and these compounds can be used alone or as a mixture of two or more.
The use amount of the neutralizing agent is preferably 0.5 to 3 equivalents, more preferably 0.7 to 1 with respect to 1 equivalent of carboxyl group and / or sulfonyl group in the polyurethane resin having the carboxyl group and / or sulfonyl group. .5 equivalents. If it is less than the above range, the stability of the aqueous resin of the urethane resin (C) in water tends to decrease.

Examples of the chain extender used in the present invention include water, ethylenediamine, diethylenetriamine, NBDA (trade name, manufactured by Mitsui Chemicals), N-methyl-3,3′-diaminopropylamine, and diethylenetriamine and acrylate. Polyamines such as adducts or hydrolysis products thereof are suitable.
Examples of the solvent used for obtaining the aqueous resin of the urethane resin (C) include ketones such as methyl ethyl ketone and acetone, esters such as methyl acetate and ethyl acetate, tetrahydrofuran, and the like. The following solvents are not particularly limited, and these solvents can be used alone or in a mixed state of two or more. Use of a solvent having a boiling point exceeding 100 ° C., that is, exceeding the boiling point of water, makes it difficult to completely distill off only the solvent from the solution after forming the aqueous resin, and the high boiling point solvent remains in the film. Since it affects physical properties, when it is unavoidably used for performance, it is preferably used in an amount of 10 parts by weight or less based on 100 parts by weight of the aqueous resin of the urethane resin (C).

Moreover, the aqueous resin of the urethane resin (C) used by this invention can be used also as a modified body by making it react with other components, such as another monomer and a resin component. Further, in the aqueous resin of urethane resin (C) obtained in the present invention, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate, ethylene, propylene It can also be used as a complex obtained by polymerizing at least one monomer such as itaconic acid and maleic acid.
Among the aqueous resins of the urethane resin (C) thus obtained, the elongation at break is preferably 0.1 to 800%. Furthermore, in order to improve the stability to water, the said surfactant can be used.

[Petroleum hydrocarbon resin (D)]
Examples of the petroleum hydrocarbon resin (D) used in the present invention include an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and their Copolymeric alicyclic. C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) C9 fraction copolymerized resin), styrene, indene, coumarone, coumarone indene resin containing dicyclopentadiene, etc., and condensation of ρ-tertiarybutylphenol and acetylene. Examples thereof include alkylphenol resins typified by products, xylene resins obtained by reacting o-xylene, ρ-xylene, and m-xylene with formalin. These can be used alone or in combination of two or more. Among these, petroleum hydrocarbon resins having a weight average molecular weight of 1,000 to 50,000 as measured by GPC are preferable, and 1,500 to 30,000 are particularly preferable. Moreover, what has a polar group in these resin is still more preferable.

[Rosin resin (E)]
Examples of the rosin resin (E) used in the present invention include modified rosin modified with natural rosin, polymerized rosin, maleic acid, fumaric acid, (meth) acrylic acid and the like. Examples of the rosin derivative include esterified products, phenol-modified products and esterified products of the above rosins, and hydrogenated products thereof can also be mentioned.

[Terpene resin (F)]
Examples of the terpene resin (F) used in the present invention include resins comprising α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, and the like. Α-pinene, β-pinene, Examples thereof include aromatic-modified terpene resins obtained by polymerizing aromatic monomers such as styrene on limonene, dipentene, and the like, and hydrogenated products thereof can also be mentioned. Among these, terpene phenol resins, aromatic modified terpene resins, and hydrogenated products thereof are preferable.
In the present invention, petroleum hydrocarbon resin (D), rosin resin (E), terpene resin
(F) can also be used in combination.

The present invention relates to the aqueous resin (A), the aqueous resin (B) and / or (C), the petroleum hydrocarbon resin (D) and / or the rosin resin (E) and / or the terpene. An aqueous resin of the resin (F) can be mixed. The mixing ratio of (B) and / or (C) is preferably 1 to 90 parts by weight, and more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the solid content of (A).
Further, an aqueous resin such as petroleum hydrocarbon resin (D) and / or rosin resin (E) and / or terpene resin (F) may be mixed. The mixing ratio is preferably 1 to 95 parts by weight of (D) and / or (E) and / or (F), more preferably 5 to 80 parts per 100 parts by weight of the solid content of (A). Part by weight is preferred.

Among the coating materials of the present invention, a composition having active hydrogen and / or hydroxyl groups can use a curing agent capable of reacting with active hydrogen and / or hydroxyl groups.
For example, it can be used by mixing with a curing agent having an isocyanate group in the molecule. As the curing agent, Takenate WB series (Mitsui Takeda Chemical Co., Ltd.), Elastron BN series (isocyanate group treated with blocking agents such as oximes, lactams, phenols, etc.) Daiichi Kogyo Seiyaku Co., Ltd.).
A resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril, and formaldehyde and formaldehyde, for example, a part of a methylol group by a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc. Alternatively, amino resins which are all alkyl etherified can also be used as the curing agent.

An oxazoline compound can also be used as a curing agent. Examples of the curing agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2- Examples thereof include isopropenyl-4-methyl-2-oxazoline.
Furthermore, a carbodiimide compound can also be used as a curing agent. The curing agent is not particularly limited as long as it contains two or more carbodiimide groups in one molecule and has a water-soluble or water-dispersible carbodiimide resin. As the carbodiimide resin, an arbitrary one can be appropriately selected from known ones, and examples thereof include Nisshinbo Holdings' carbodilite.

The curing agent capable of reacting with the aqueous resin of the present invention and active hydrogen and / or hydroxyl group can be used in an arbitrary ratio.
When the curing agent capable of reacting with active hydrogen and / or hydroxyl group is a curing agent having an isocyanate group, the mixing ratio of active hydrogen and isocyanate group is 0.5: 1.0 to 1.0: The range of 0.5 is preferable, and the range of 0.8: 1.0 to 1.0: 0.8 is more preferable.
Further, when the curing agent capable of reacting with active hydrogen and / or hydroxyl group is an amino resin, it is preferably used in the range of 95/5 to 20/80 by weight ratio of the aqueous resin / amino resin solid of the present invention. The range of 90/10 to 60/40 is more preferable.

Further, when the curing agent capable of reacting with active hydrogen and / or hydroxyl group is an oxazoline compound, it is preferably used in the range of 95/5 to 20/80 by weight ratio of the aqueous resin / amino resin solid of the present invention. The range of 90/10 to 60/40 is more preferable.
Furthermore, when the curing agent capable of reacting with active hydrogen and / or hydroxyl groups is a carbodiimide compound, the weight ratio of the aqueous resin / carbodiimide resin solid of the present invention is 97/3 to 70/30. The range of 95/5 to 80/20 is more preferable.

The mixture of the curing agents described above can be coated and cured as it is, but a reactive catalyst can be used in combination as necessary.
Other slipperiness imparting agents (for example, synthetic wax, natural wax, etc.), tackiness imparting agents, crosslinking agents, film forming aids, leveling agents, viscoelasticity modifiers, wetting agents, flame retardants (if necessary) For example, phosphorus-containing resins such as ammonium polyphosphate, phosphate esters, melamine, zinc borate, magnesium hydroxide, etc.), stabilizers, rust inhibitors, fungicides, UV absorbers, weather stabilizers, heat stabilizers , Foaming agent, antifoaming agent, wetting agent, coagulant, gelling agent, anti-aging agent, softening agent, plasticizer, flavoring agent, anti-sticking agent, mold release agent, anti-settling agent, antioxidant, charging Additives such as inhibitors, dyes, pigments), fillers, organic solvents, oils (mineral lubricants, mineral oils, synthetic oils, vegetable oils, etc.) may be added as long as the object of the present invention is not impaired. . These additives may be used alone or in combination of two or more.

  The coating method of the aqueous resin of the present invention, or a mixture of the aqueous resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or hydroxyl group is not particularly limited, but is preferably performed by spray coating, For example, it can be applied by spraying on the surface to be coated with a spray gun. The application can usually be carried out easily at room temperature, and the drying method after application is not particularly limited, and it can be dried by an appropriate method such as natural drying or heat forced drying.

In addition to the above, the aqueous resin of the present invention or the aqueous resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, in addition to the above, is based on an aqueous epoxy resin, aqueous polyester, aqueous alkyd Resins or paints containing these resins can be mixed and used. These may be used alone or in combination of two or more.
In particular, the water-based resin of the present invention or the water-based resin of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group has high adhesion to polypropylene, especially various engineered plastics, because of its properties. Expresses sex.
Examples of engineer plastics include polyamides such as nylon, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyphenylene sulfide, polyether ether ketone, polyether nitrile, polycarbonate, modified polyphenylene ether, polysulfone, polyether sulfone, polyarylate, and polyamideimide. , Polyetherimide, polyimide, polymethylpentene, polybenzimidazole, etc., and various stabilizers such as antioxidants, weather resistance stability, heat-proofing agents, colorants such as inorganic pigments and organic pigments, carbon It can also be used for those added with conductivity imparting agents such as black and ferrite, and other inorganic and organic additives.

Hereinafter, although the manufacturing method and various test examples of the composition of this invention are given and demonstrated further, this invention is not limited at all by these Examples.
In the following, parts and percentages are by weight unless otherwise specified.
Production of thermoplastic elastomer (A) <Production Example 1>
Into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 833 ml of dry hexane, 100 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, and then the temperature inside the polymerization apparatus was raised to 70 ° C. with propylene. After pressurizing the system pressure to 0.55 MPa, the system pressure was adjusted to 0.76 MPa with ethylene. Subsequently, 0.001 mmol of diphenylmethylene (3-tert-butyl-5-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (Tosoh) in terms of aluminum・ Toluene solution brought into contact with Finechem) was added to the polymerization vessel, polymerization was performed for 25 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 0.76 MPa with ethylene, and 20 ml of methanol was added to terminate the polymerization. did. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 137.7 g, the ethylene content was 14 mol%, the butene content was PBER consisting of 19 mol%, the molecular weight (Mw) measured by GPC was 350,000, and the molecular weight distribution (Mw / Mn) Was 2.0. The mm value was 90%. Further, a clear melting peak could not be confirmed in the heat of fusion by DSC measurement.

<Production Example 2>
20 parts by weight of homopolypropylene having a melting point of 163 ° C., an MFR of 7 g / 10 min, and a propylene content of 99 mol% or more were melt-kneaded with 80 parts by weight of PBER synthesized in Production Example 1 to obtain composition pellets.
<Production Example 3>
80 parts by weight of PBER synthesized in Production Example 1 was melted with 20 parts by weight of random polypropylene having a melting point of 140 ° C., MFR of 7 g / 10 min, a propylene content of 96.3 mol%, an ethylene content of 2.2 mol% and a butene content of 1.5 mol%. The mixture was kneaded to obtain composition pellets.
<Production Example 4>
Using a Henschel mixer, 100 parts by weight of the resin obtained in Production Example 3, 1 part by weight of maleic anhydride, 0.08 part by weight of 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3 After mixing, graft modification was performed using an extruder set at a cylinder temperature of 240 ° C. to obtain composition pellets.

<Production Example 5>
Into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 866 ml of dry hexane, 90 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, and then the temperature inside the polymerization apparatus was raised to 65 ° C. The pressure in the system was increased and adjusted to 0.7 MPa. Next, a toluene solution obtained by contacting 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride with 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum. Was added to the polymerization vessel, polymerization was carried out for 30 minutes while maintaining the internal temperature at 65 ° C. and the internal pressure at 0.76 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 12.5 g, butene content was PBR consisting of 27.9 mol%, the molecular weight (Mw) measured by GPC was 250,000, and the molecular weight distribution (Mw / Mn) was 2.0. The melting point by DSC measurement was 74.4 ° C.

<Production Example 6>
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube was charged with 300 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 75 ° C. while purging with nitrogen under stirring. The internal temperature is maintained at 75 ° C., 2 g of potassium persulfate as a polymerization initiator is added, and after dissolution, 250 g of ion exchange water, 1 g of sodium lauryl sulfate, 9 g of acrylamide, 200 g of styrene, 220 g of 2-ethylhexyl acrylate, methacrylic acid An emulsion prepared by adding 9 g with stirring was dropped into a reaction vessel continuously over 6 hours for polymerization. After completion of the dropwise addition, aging and neutralization for 5 hours gave a water-based resin (C) made of a monomer having an α, β-monoethylenically unsaturated group. The obtained aqueous resin had a solid content concentration of 40%, a pH of 8, and an average particle size of 0.2 μm.

<Production Example 7>
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, 399.5 g of polytetramethylene ether glycol (Hodogaya Chemical Co., Ltd., PTG2000SN), 2,2-dimethylolbutanoic acid 14. 0 g, 1,4-butanediol 16.6 g, hexamethylene diisocyanate 96.3 g and methyl ethyl ketone 374.0 g were charged and reacted at 90 ° C. for 6 hours in a nitrogen gas atmosphere. Then, it cooled to 60 degreeC, 13.3 g of triethylamine was added, and it mixed for 30 minutes under this temperature. The obtained prepolymer was mixed and stirred with 1275.7 g of 0.86% hexamethylenediamine aqueous solution, and then methyl ethyl ketone was removed under reduced pressure at 60 ° C., so that the solid content was 30% and the solid content acid value was 10 KOH mg. / G, pH: 8, average particle diameter: 0.2 micrometer urethane resin (C) aqueous resin was obtained.

<Production Example 8>
A four-necked flask equipped with a stirrer, thermometer, reflux cooling device, and nitrogen inlet tube was charged with 300 parts of hexane and 300 parts of petroleum resin (manufactured by Mitsui Chemicals, Hilets T-480X), and heated under reflux. Dissolved. 500 parts of this solution, 250 parts of ion-exchanged water, and 1.5 parts of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neopelex F-25) were mixed and stirred at a rotational speed of 10,000 rpm for 15 minutes. Next, 0.7 part of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., Hibiswaco 304) was added and mixed by stirring to obtain an emulsion. Hexane in this emulsion was distilled off under reduced pressure with an evaporator to obtain a water-based resin of petroleum hydrocarbon resin (D) having a solid content of 50%.

Example 1
Anhydrous maleic as propylene-based resin (a-5) containing 100 parts by weight of the resin obtained in Production Example 1 as an unmodified thermoplastic elastomer (a-1) and a group of a carboxylic acid or a salt thereof bonded to a polymer chain A mixture of 10 parts by weight of acid-modified polypropylene wax (manufactured by Mitsui Chemicals, High Wax NP0555A) and 3 parts by weight of potassium oleate as an anionic surfactant (H) is a twin-screw extruder (Ikekai Tekko Co., Ltd.) It is supplied at a rate of 3000 g / hour from a hopper of PCM-30, L / D = 40) manufactured by the company, and a 15% aqueous solution of dimethylethanolamine is 150 g / hour from a supply port provided in the vent portion of the extruder. The mixture was continuously fed at a rate and continuously extruded at a heating temperature of 230 ° C. The extruded resin mixture is further obtained by adding a solid emulsion extruded from the tip of a 40 mmφ single screw extruder (L / D = 27, barrel temperature: 120 ° C.) connected to the tip of the twin screw extruder to 80 Aqueous resin-1 was obtained by pouring into warm water at 0 ° C. The obtained water-based resin-1 had a yield of 99%, a solid content concentration of 45%, a pH of 10, and an average particle size of 0.4 μm (measured by Microtrac).
Except for changing the unmodified thermoplastic elastomer (a-1) to the resin obtained in Production Example 5, an aqueous resin-2 was obtained by the production method of the aqueous resin-1. The obtained water-based resin-2 had a yield of 99%, a solid content concentration of 45%, a pH of 10, and an average particle size of 0.4 μm.
70 parts by weight of the aqueous resin-1 and 30 parts by weight of the aqueous resin-2 were stirred and mixed at room temperature to obtain an aqueous resin.

Example 2
Aqueous resin-3 was obtained in the same manner as in Example 1 except that the unmodified thermoplastic elastomer (a-1) of aqueous resin-1 was changed to the resin obtained in Production Example 2. The obtained water-based resin-3 had a yield of 99%, a solid content concentration of 45%, a pH of 10, and an average particle size of 0.4 μm.
70 parts by weight of the aqueous resin-3 and 30 parts by weight of the aqueous resin-2 described in Example 1 were stirred and mixed at room temperature to obtain an aqueous resin.

Example 3
Aqueous resin-4 was obtained in the same manner as in Example 1, except that the unmodified thermoplastic elastomer (a-1) of aqueous resin-1 was changed to the resin obtained in Production Example 3. The obtained water-based resin-4 had a yield of 99%, a solid content concentration of 45%, a pH of 10, and an average particle size of 0.4 μm.
70 parts by weight of the aqueous resin-4 and 30 parts by weight of the aqueous resin-2 described in Example 1 were stirred and mixed at room temperature to obtain an aqueous resin.

Example 4
Anhydrous maleic anhydride as a propylene resin (a-5) containing 100 parts by weight of the resin obtained in Production Example 4 as an unmodified thermoplastic elastomer (a-1) and a carboxylic acid or salt group bonded to the polymer chain A mixture of 30 parts by weight of acid-modified polypropylene wax (manufactured by Mitsui Chemicals, High Wax NP0555A) and 8 parts by weight of potassium oleate as an anionic surfactant (H) is a twin screw extruder (Ikekai Tekko Co., Ltd.) It is supplied at a rate of 3000 g / hour from a hopper of PCM-30, L / D = 40) manufactured by the company, and a 30% aqueous solution of aminomethylpropanol is supplied at a rate of 500 g / hour from a supply port provided in the vent portion of the extruder. The mixture was continuously fed at a rate and continuously extruded at a heating temperature of 230 ° C. The extruded resin mixture is further obtained by adding a solid emulsion extruded from the tip of a 40 mmφ single screw extruder (L / D = 27, barrel temperature: 120 ° C.) connected to the tip of the twin screw extruder to 80 The mixture was poured into warm water at 0 ° C. to obtain an aqueous resin-5. The obtained aqueous resin-5 had a yield of 99%, a solid content concentration of 35%, a pH of 11, and an average particle size of 0.1 μm (measured by Microtrac).
70 parts by weight of the aqueous resin-5 and 30 parts by weight of the aqueous resin-2 described in Example 1 were stirred and mixed at room temperature to obtain an aqueous resin.

Example 5
Anhydrous maleic anhydride as propylene-based resin (a-5) containing 100 parts by weight of the resin obtained in Production Example 3 as an unmodified thermoplastic elastomer (a-1) and a carboxylic acid or salt group bonded to a polymer chain A mixture of 10 parts by weight of acid-modified polypropylene wax (manufactured by Mitsui Chemicals, high wax NP0555A) and 10 parts by weight of montanic acid (manufactured by Clariant Japan Co., Ltd., Ricowax S) as a higher fatty acid (a-6), Dimethylethanolamine is supplied from a hopper of a twin screw extruder (Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40) at a speed of 3000 g / hour, and from a supply port provided in a vent portion of the extruder. 15% aqueous solution was continuously fed at a rate of 300 g / hr and continuously extruded at a heating temperature of 230 ° C. The extruded resin mixture is further obtained by adding a solid emulsion extruded from the tip of a 40 mmφ single screw extruder (L / D = 27, barrel temperature: 120 ° C.) connected to the tip of the twin screw extruder to 80 The mixture was poured into warm water at 0 ° C. to obtain an aqueous resin-6. The obtained water-based resin-6 had a yield of 99%, a solid content concentration of 45%, a pH of 10, and an average particle size of 0.4 μm (measured by Microtrac).
70 parts by weight of the aqueous resin-6 and 30 parts by weight of the aqueous resin-2 described in Example 1 were stirred and mixed at room temperature to obtain an aqueous resin.

Example 6
A pressurized reaction vessel was charged with 140 parts of the propylene-based resin obtained in Production Example 1 and 680 parts of toluene, and the interior of the vessel was heated to 145 ° C. while purging with nitrogen, and then 1.6 parts of 2-hydroxyethyl acrylate was added to toluene. The mixture was mixed with 20 parts, and 1.1 parts of di-tert-butyl peroxide was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was kept at 140 ° C. for 2 hours and then cooled, 44.1 parts of PTG2000, 1.2 parts of 1,6-hexanediol, 3.7 parts of 2,2-dimethylolbutanoic acid, 11.1 parts of 6-hexamethylene diisocyanate and 0.11 parts of dibutyltin laurate were charged and reacted at 90 ° C. for 8 hours in a nitrogen gas atmosphere. The obtained polymer was heated to 140 ° C. in a pressure reaction vessel, 1.0 part of di-tert-butyl peroxide was added dropwise over 2 hours, and held at a temperature of 140 ° C. for 2 hours. After cooling this to 60 ° C. and neutralizing triethylamine to theoretically 100%, 300 parts of ion-exchanged water and 0.5 g of sodium dodecylbenzenesulfonate were further mixed, and the mixture was mixed at 15 rpm at 10000 rpm. The mixture was stirred for a minute to obtain an emulsion. Toluene in this emulsion was distilled off under reduced pressure with an evaporator to obtain an aqueous resin-7 containing a propylene resin having a solid content of 40%.
70 parts by weight of the aqueous resin-7 and 30 parts by weight of the aqueous resin-2 described in Example 1 were stirred and mixed at room temperature to obtain an aqueous resin.

Example 7
100 parts by weight of the water-based resin obtained in Example 1, 90 parts by weight of the water-based resin of the urethane resin (C) obtained in Production Example 6, and Nanolet R1050 (manufactured by Yasuhara Chemical Co., Ltd.), which is a water-based resin of the terpene resin (F) ) 80 parts by weight and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.

Example 8
An aqueous resin having a solid content of 35% was obtained in the same manner as in Example 7, except that the aqueous resin obtained in Example 1 was changed to the aqueous resin obtained in Example 2.
Example 9
An aqueous resin having a solid content of 35% was obtained in the same manner as in Example 7, except that the aqueous resin obtained in Example 1 was changed to the aqueous resin obtained in Example 3.
Example 10
An aqueous resin having a solid content of 35% was obtained in the same manner as in Example 7, except that the aqueous resin obtained in Example 1 was changed to the aqueous resin obtained in Example 4.
Example 11
An aqueous resin having a solid content of 35% was obtained in the same manner as in Example 7, except that the aqueous resin obtained in Example 1 was changed to the aqueous resin obtained in Example 5.
Example 12
An aqueous resin having a solid content of 35% was obtained in the same manner as in Example 7, except that the aqueous resin obtained in Example 1 was changed to the aqueous resin obtained in Example 6.
Example 13
In the same manner as in Example 9, except that the aqueous resin of the terpene resin (F) in Example 9 was changed to Superester E720 (manufactured by Arakawa Chemical Industries, Ltd.), which is an aqueous resin of the rosin resin (E). An aqueous resin having a solid content of 35% was obtained.
Example 14
Except for changing the aqueous resin of the terpene resin (F) of Example 9 to the aqueous resin of the petroleum hydrocarbon resin (D) emulsified in Production Example 8, a solid content of 35% was obtained in the same manner as in Example 9. An aqueous resin was obtained.

Example 15
Except for changing the aqueous resin of urethane resin (C) of Example 9 to 68 parts by weight of aqueous resin of acrylic resin (B) obtained in Production Example 7, the solid content was 35% in the same manner as in Example 9. An aqueous resin was obtained.
Example 16
100 parts by weight of the aqueous resin obtained in Example 3, 50 parts by weight of the aqueous resin of the urethane resin (C) obtained in Production Example 6, and Nanolet R1050 (Yasuhara Chemical Co., Ltd.), which is an aqueous resin of the terpene resin (F) ) 45 parts by weight and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Example 17
50 parts by weight of water-based resin-4 described in Example 3, 50 parts by weight of water-based resin-2 described in Example 1, 90 parts by weight of water-based resin of urethane resin (C) obtained in Production Example 6, terpene system 80 parts by weight of Nanolet R1050 (manufactured by Yasuhara Chemical Co., Ltd.), which is an aqueous resin of resin (F), and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Example 18
20 parts by weight of aqueous resin-4 described in Example 3, 80 parts by weight of aqueous resin-2 described in Example 1, 90 parts by weight of aqueous resin of urethane resin (C) obtained in Production Example 6, terpene system 80 parts by weight of Nanolet R1050 (manufactured by Yasuhara Chemical Co., Ltd.), which is an aqueous resin of resin (F), and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.

Comparative Example 1
The aqueous resin-1 described in Example 1 and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Comparative Example 2
The aqueous resin-2 described in Example 2 and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Comparative Example 3
The aqueous resin-3 described in Example 2 and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Comparative Example 4
The aqueous resin-4 described in Example 2 and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Comparative Example 5
The aqueous resin-5 described in Example 2 and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.
Comparative Example 6
The aqueous resin-6 described in Example 2 and ion-exchanged water were mixed at room temperature to obtain an aqueous resin having a solid content of 35%.

Comparative Example 7
Melting point 140 ° C., MFR 7 g / 10 min, propylene content 96.3 mol%, ethylene content 2.2 mol%, butene content 1.5 mol% 100 parts by weight of random polypropylene, high wax NP0555A 10 parts by weight and potassium oleate 3 A mixture of parts by weight is supplied at a rate of 3000 g / hr from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40), and is supplied to the vent part of the extruder. From the supply port provided, a 15% aqueous solution of dimethylethanolamine was continuously supplied at a rate of 150 g / hour and continuously extruded at a heating temperature of 230 ° C. The extruded resin mixture is a solid emulsion extruded from the tip of a 40 mmφ single screw extruder (L / D = 27, barrel temperature: 140 ° C.) connected to the tip of the twin screw extruder, and further 80 It could be poured into warm water at ℃. The obtained water-based resin had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.

Comparative Example 8
A water-based resin was obtained in the same manner as in Comparative Example 1 except that the random polypropylene was changed to polyethylene having a melting point of 86 ° C. and MFR of 7 g / 10 min. The obtained aqueous resin had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.

[Evaluation and results]
<Sprayability of water-based resin>
Using a paint gun (Iwata Co., Ltd. Wider spray gun (trade name: W-88-13H5G)), atomizing pressure 4 kg / cm 2, nozzle one rotation opening, at a temperature of 30 ° C. in the painting booth, Spray the water-based resin obtained in Examples and Comparative Examples and observe whether stringing occurs or not. did.

<Physical properties of coating film>
Evaluation on various base materials 100 parts of the aqueous resin obtained in Examples and Comparative Examples were added with 2 parts of Olfin E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) as a wetting agent, and the surface was wiped with isopropyl alcohol. Homopolypropylene, Arene (Mitsui Chemicals Co., Ltd., aromatic polyamide), nylon 6, nylon 66, polyphenylene sulfide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and a film thickness after drying of 10 μm After each coating, the sample was placed in an oven at 80 ° C. and treated for 30 minutes to prepare test piece-1.
Further, on this coating film, a two-component solvent-based resin (manufactured by Mitsui Chemicals, Inc., trade name: Olester Q186 (main agent) / Takenate D-160N (compound)), OH / NCO = 0.85 The film was dried to give a film thickness of 40 μm to form a coating film, left at room temperature for 10 minutes, then placed in an oven at 80 ° C. for 30 minutes, and a test piece -2 was created.
These test pieces were subjected to a cross peel test after 24 hours, and the results are shown in the table.
In addition, about the external appearance of a coating film, it evaluated only about the coating film after apply | coating and drying on Allen, and what is forming into a film is (circle), and what is forming a film but there is a crack is △ The case where no film was formed was rated as x. In addition, for the cross-cut peel test, a test piece with a cross cut was prepared according to the cross-cut peel test method described in JIS-K-5400, and Cellotape (registered trademark) (Nichiban Co., Ltd.) After being pasted on the grid, it was quickly pulled and peeled in the 90 ° direction, and the number of grids that were not peeled out of 100 grids was evaluated. The test was performed 5 times, and those that did not peel were further peeled with an adhesive tape (manufactured by Nichiban). The evaluation results are ◎ for adhesive tape and cello tape (registered trademark) that do not peel, ◎ for cello tape (registered trademark) that does not peel, but peeled off the adhesive tape, The case where peeling of 1 to 10 squares was caused by peeling of the adhesive tape and cello tape (registered trademark) was Δ, and the case where peeling was caused within 4 times by peeling of the cello tape (registered trademark) was rated as x.
The results are shown in Tables 1 and 2.

Claims (10)

The thermoplastic elastomer (A) comprises an unmodified thermoplastic elastomer (a-1) and / or a monomer (b-1) or (b-1) having an α, β-monoethylenically unsaturated group. A thermoplastic elastomer (a-2) modified with a resin (B) and / or a thermoplastic elastomer (a-3) modified with a urethane resin (C),
The thermoplastic elastomer (A1) -containing water-based resin including the unmodified thermoplastic elastomer (a-1-1) satisfying the following (i) to (iii), and the following (i) and (ii) A coating material obtained by mixing two types of water-based resins of thermoplastic elastomer (A2) -containing water-based resin including unmodified thermoplastic elastomer (a-1-2) satisfying (iv).
(I) At least one copolymer of propylene and an α-olefin having 4 to 20 carbon atoms other than propylene, containing 53 mol% or more of propylene, 1 to 47 mol% of α-olefin having 4 to 20 carbon atoms, ethylene A propylene polymer having a content of 0 to 25 mol%.
(Ii) The weight average molecular weight by gel permeation chromatography (GPC) is 50,000 or more and 800,000 or less.
(Iii) No melting point is observed by differential scanning calorimetry (DSC).
(Iv) Melting point measured by differential scanning calorimetry (DSC) is less than 100 ° C. The coating material according to claim 1, wherein the water-based resin containing the thermoplastic elastomer (A1) further contains isotactic polypropylene (a-4). The solid content of the water-based resin containing the thermoplastic elastomer (A1) is 70 to 99% by weight of the total of the (a-1), (a-2), and (a-3), isotactic polypropylene (a The coating material according to claim 2, wherein -4) is 1 to 30% by weight. The monomer (b-1) having an α, β-monoethylenically unsaturated group (a-2) is at least one active hydrogen group selected from a hydroxyl group, a carboxyl group, and an amino group. The coating material according to 1. An aqueous resin comprising the thermoplastic elastomer (A) according to claim 1 and a resin (B) aqueous resin and / or urethane resin (C) comprising a monomer having an α, β-monoethylenically unsaturated group. A coating material comprising a mixture of a water-based resin and a water-based resin of petroleum-based hydrocarbon resin (D) and / or rosin-based resin (E) and / or terpene-based resin (F). 1 to 90 parts by weight of the resin (B) and / or the resin (C) with respect to 100 parts by weight of the solid content of the water-based resin containing the thermoplastic elastomer (A) according to claim 1, and the resin (D ) And / or the resin (E) and / or the resin (F) are mixed so as to be 1 to 95 parts by weight. The water-based resin containing the thermoplastic elastomer (A) according to claim 1 is an unmodified thermoplastic elastomer (a-1) and / or a monomer (b-1) having an α, β-monoethylenically unsaturated group. ) Or (b-1) modified thermoplastic elastomer (a-2) with resin (B) and the carboxylic acid or salt group bonded to the polymer chain is represented by the formula (1) -C per gram of resin. -O-
・ ・ ・ (1)
O
A group of propylene-based resin (a-5) and / or a higher fatty acid or a salt thereof (a-6) which is contained at a concentration of 0.05 to 5 mmol equivalent in terms of the group represented by the formula (a-2) The coating material according to any one of claims 1 to 6, wherein in the case where is a propylene-based resin containing a group of carboxylic acid or a salt thereof, the weight average molecular weight is larger than that of (a-5). The thermoplastic elastomer (A) is a total of 100 parts by weight of the (a-1) and the (a-2), and the (a-5) and / or (a-6) is 0.3 to 100 parts by weight. The coating material according to claim 7. The coating material according to claim 7 or 8, wherein the water-based resin containing the thermoplastic elastomer (A) according to claim 1 further contains an anionic and / or nonionic surfactant (H). The coat according to claim 9, wherein the thermoplastic elastomer (A) is 0.3 to 40 parts by weight with respect to a total of 100 parts by weight of the (a-1) and (a-2). Wood.