JP6862387B2 - Compositions, coating agents and polyolefin moldings - Google Patents

Description

The present invention relates to compositions, coating agents and polyolefin moldings.

Polyolefin resins are excellent in moldability, rigidity, heat resistance, chemical resistance, electrical insulation, etc., and are inexpensive. Therefore, they are widely and widely used as molded products of films, fibers, and other various shapes. There is.
On the other hand, the polyolefin resin is a so-called non-polar resin having no polar group in the molecule, and has a problem that the dyeability is poor and the dye cannot be directly applied.

Conventionally, as a method of imparting dyeability to a polyolefin resin, for example, a method of bringing a polyamine compound into contact with a polyolefin resin whose surface has been activated (see Patent Document 1) is known. However, this method has a problem that the polyamine compound has a weak ability to adsorb to polyolefin, and the dye is immediately removed by an external stimulus such as washing or rubbing, so that sufficient dyeing fastness cannot be obtained.
Further, in addition to dyeing with a dye, a method of dispersing a pigment in a polyolefin resin in advance (see Patent Document 2) is also known, but it is difficult to obtain a clear color and the mechanical strength (impact resistance) of the polyolefin resin (impact resistance). And flexibility, etc.), and there was a problem that improvement was eagerly desired.

In order to solve the above problems, modification of a sulfonic acid (salt) -modified polyolefin resin by copolymerizing an unsaturated (poly) carboxylic acid (anhydrous), a sulfonic acid (salt) having a polymerizable unsaturated group, and a polyolefin. A method of mixing an agent with a polyolefin resin to improve dyeability (see Patent Document 3) has been proposed. However, the introduction of a sulfonic acid (salt) group improves the dyeability only in the case of a cationic dye, and there is a problem that it cannot be applied to other dyes.

Japanese Unexamined Patent Publication No. 2008-255207 JP-A-2007-254929 Japanese Unexamined Patent Publication No. 2014-185399

An object of the present invention is to provide a composition that imparts excellent dyeability and washing fastness to a polyolefin resin.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems. That is, the present invention is the group of the acid-modified polyolefin (A), an amine compound having at least three amino groups (B), and an anionic surfactant (C1),及Beauty nonionic surfactant (C4) contains at least one surfactant (C) selected from,
The anionic surfactant (C1) is a fatty acid salt and / or a sulfonic acid having an alkyl group having 8 to 24 carbon atoms.
Said nonionic surfactant (C4) is higher alcohol AO (two to four carbon atoms) adduct (addition molar number of 1 to 30 per active hydrogen) der Ru composition (8 to 32 carbon atoms) ; of compounds and (AxB), anionic surfactant (C1), containing at least one surfactant selected from the group consisting及beauty nonionic surfactant (C4) (C),
The anionic surfactant (C1) is a fatty acid salt and / or a sulfonic acid having an alkyl group having 8 to 24 carbon atoms.
Said nonionic surfactant (C4) is higher alcohol AO (two to four carbon atoms) adduct (addition molar number of 1 to 30 per active hydrogen) der Ru composition (8 to 32 carbon atoms) And
The compound (AxB) is a compound obtained by cross-linking an acid-modified polyolefin (A) and an amine compound (B) having at least three amino groups with a cross-linking agent (x).
A composition in which the cross-linking agent (x) satisfies at least one of the following (i) to (ii); a coating agent containing the composition; a polyolefin molded product containing the composition; coating with the coating agent. Polyolefin molded product having a film; a polyolefin molded product having a coating film containing the composition.
(I)
The cross-linking agent (x) has at least two groups selected from the group consisting of an epoxy group, an isocyanate group and a blocked isocyanate group in one molecule.
(Ii)
Crosslinker (x) has at least one carbodiimide group in one molecule.

The composition of the present invention imparts excellent dye dyeability and washing fastness to the polyolefin resin. In addition, the polyolefin molded product containing the above composition is excellent in dyeability and washing fastness.

The composition of the present invention is the composition of the following first, second and third inventions.

First, the composition which is the first invention of this invention will be described.
The composition of the first invention comprises an acid-modified polyolefin (A), an amine compound (B) having at least three amino groups, an anionic surfactant (C1), a cationic surfactant (C2), and amphoteric tenside. It contains at least one surfactant (C) selected from the group consisting of a surfactant (C3) and a nonionic surfactant (C4).

Hereinafter, the acid-modified polyolefin (A) as an essential component, the amine compound (B) having at least three amino groups, and the surfactant (C) will be described in sequence.

The acid-modified polyolefin (A) in the present invention is a polyolefin resin having an acid group in the molecule. As the above (A), polyolefins having no acid group [polyolefins (E1) and (E2) described later] are abbreviated as carbon-carbon double bonds (hereinafter, “C = C bond”) in the molecule. Examples thereof include those modified with the compound (a) having both an acid group and an acid group.
Examples of the acid group include a carboxy group and a sulfo group, an acid anhydride group thereof, and a salt thereof (alkali metal salt, etc.). Of these, a carboxy group and an acid anhydride group thereof are preferable from the viewpoint of reactivity with an amino group.

Specific examples of the acid-modified polyolefin (A) in the present invention include unsaturated (poly) carboxylic acid (anhydrous) modified products and unsaturated (poly) sulfonic acid modified products of polyolefins, which are dyeable. From the above viewpoint, preferred examples thereof include (meth) acrylic acid-modified polyolefin, (anhydrous) maleic acid-modified polyolefin, fumaric acid-modified polyolefin and (meth) allylsulfonic acid-modified polyolefin.
Examples of the polyolefin having an acid group in the molecule include those in which the compound (a) is added to the polyolefin molecular chain and / or the end of the molecular chain, those in which the compound (a) is graft-copolymerized with the polyolefin molecule, and polyolefin. Examples thereof include a block copolymerization of the molecule and the compound (a).
Of these, from the viewpoint of dispersibility in water of (A) and color uniformity of the coating product, the compound (a) added to the polyolefin molecule terminal (that is, an acid group is added to the polyolefin molecule terminal). What you have) is preferable.

As the acid-modified polyolefin (A), a manufactured product or a commercially available product may be used, and the production method for producing the acid-modified polyolefin (A) is not limited, but the following methods and the like can be mentioned. Be done.
(1) A method of radically polymerizing a polyolefin (E1) having no C = C bond in the molecule and a compound (a) having both a C = C bond and an acid group in the molecule in the presence of a radical initiator. (2) Presence of a radical initiator containing more than 0.3% by weight of the polyolefin (E2) having a C = C bond in the molecule and the compound (a) having both a C = C bond and an acid group in the molecule. Method of radical polymerization underneath (3) 0.3% by weight or less of a polyolefin (E2) having a C = C bond in the molecule and a compound (a) having both a C = C bond and an acid group in the molecule. Method for Addition Reaction in the Presence of the Radical Initiator or in the absence of the Radical Initiator Of these production methods, the method (3) is preferable. The above-mentioned (A) produced by the method (3) is preferable from the viewpoint of color uniformity and water dispersibility, because acid groups are likely to be selectively added to one end or both ends of the polyolefin molecule.

Examples of the compound (a) having both a C = C bond and an acid group in the molecule used in the methods (1) to (3) above include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated dicarboxylic acid anhydride. Examples thereof include compounds, unsaturated sulfonic acids and salts thereof (alkali metal salts, etc.).
Examples of the unsaturated monocarboxylic acid include a chain aliphatic unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, etc.) having 3 to 24 carbon atoms (hereinafter, may be abbreviated as C) and an alicyclic type of C7 to 24. Unsaturated monocarboxylic acid (cyclohexenecarboxylic acid, cycloheptenecarboxylic acid, bicycloheptenecarboxylic acid, methyltetrahexenecarboxylic acid, etc.) and C7-24 aromatic unsaturated monocarboxylic acid (4-vinylbenzoic acid, etc.) And so on.
Examples of the unsaturated dicarboxylic acid include a chain aliphatic unsaturated dicarboxylic acid of C4 to 24 (maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc.) and an alicyclic unsaturated dicarboxylic acid of C8 to 24 (cyclo). Examples thereof include hexendicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid and methyltetrahydrophthalic acid) and C8-24 aromatic unsaturated dicarboxylic acid (4,4'-stillbenzicarboxylic acid, etc.).
Examples of unsaturated dicarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
Examples of unsaturated sulfonic acids include C2-30 aliphatic unsaturated sulfonic acids [vinyl sulfonic acid, allyl sulfonic acid, metharyl sulfonic acid, tetradecene sulfonic acid, alkyl (C1 to 23) allyl sulfosuccinic acid and 2-acrylamide-. 2-Methylpropanesulfonic acid, etc.] and C8-24 aromatic unsaturated sulfonic acid (styrene sulfonic acid, dodecenebenzenesulfonic acid, etc.) and the like can be mentioned.
Of these, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides and salts thereof are preferable from the viewpoint of reactivity with amino groups, and maleic acid, maleic anhydride and maleic acid salts are more preferable. ..

Examples of the olefin constituting the polyolefin (E1) used in the method (1) above include alkenes of C2 to 30.
Examples of the C2-30 alkene include ethylene, propylene, 1- or 2-butene, isobutene, 1-hexene, 1-decene and 1-dodecene.

Examples of the above-mentioned polyolefin (E1) include ethylene unit-containing (co) polymers [high, medium or low density polyethylene, and unsaturated monomers of ethylene and C4 to 30 (1-butene, 2-butene and 1-). Copolymers with (hexene, etc.)], propylene unit-containing (co) copolymers [polypropylene, and unsaturated monomers of propylene and C4 to 30 (1-butene, 2-butene, 1-hexene and 1, Copolymer with 4-hexadiene, etc.], copolymer containing ethylene unit and propylene unit [propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, propylene / ethylene / 1- Alken (C = 5 to 20) copolymer, ethylene / propylene / 1,4-hexadiene copolymer, etc.], polybutene (poly-1-butene, poly-2-butene, etc.) and the like can be mentioned.
Of these, propylene / ethylene copolymers, propylene / 1-butene copolymers and propylene / ethylene / 1-butene copolymers are preferable from the viewpoint of adhesion to polypropylene, and propylene is even more preferable. It is a / 1-butene copolymer.
The "propylene / ethylene copolymer" indicates that "propylene" and "ethylene" before and after the "/" are copolymerized, and the same description method is used below.

The polyolefin (E1) can be obtained by (co) polymerizing the above-mentioned C2-30 alkene by a known method.
The polyolefin (E1) is Toughmer XM5070 [manufactured by Mitsui Chemicals Co., Ltd.], Toughmer XM5080 [manufactured by Mitsui Chemicals Co., Ltd.], VESTOPLAST750 (manufactured by Evonik), Versify 3000 [manufactured by Dow Chemicals Co., Ltd.], etc. Can be obtained from the market as.

The polyolefin (E2) having a C = C bond used in the methods (2) and (3) above preferably has a C = C bond at the molecular end.
The number of C = C bonds contained in the polyolefin (E2) is preferably 0.1 to 20 per 1,000 carbons from the viewpoint of copolymerizability with (a) and addition reactivity. The number is more preferably 0.3 to 18, and particularly preferably 0.5 to 15.
Here, the number of C = C bonds is an integral value of the peak (4.6 to 4.8 ppm) derived from the double bond obtained from the spectrum ^{of 1 H-NMR (nuclear magnetic resonance) spectroscopy of polyolefin (E2).} Can be calculated from.

The polyolefin (E2) having a C = C bond in the molecule can be obtained by producing it by a known production method such as the following polymerization method and heat reduction method.

Examples of the polymerization method include a method in which an unsaturated group remains in the skeleton by using a diene or the like as a monomer.

As a heat-decomposing method, the above-mentioned polyolefin (E1) is continuously or discontinuously subjected to nitrogen aeration, in the absence of organic peroxide, at a temperature of 300 ° C. or higher and 450 ° C. or lower for 0.5 to 10 hours. A method of heat-decomposing (heat-decomposing method 1); and a method of continuously or discontinuously heat-decomposing at a temperature of 180 ° C. or higher and lower than 300 ° C. for 0.5 to 10 hours in the presence of organic peroxide (heat-decomposing method 1) The heat reduction method 2) and the like can be mentioned.
In both cases (heat reduction method 1) and (heat reduction method 2), a continuous heat reduction method is preferable from an industrial point of view.
Of these (heat reduction method 1) and (heat reduction method 2), the method in which a larger number of C = C bonds at the molecular ends is easily obtained (heat reduction method 1) is preferable.

Among the methods for producing these polyolefins (E2), those having a larger number of C = C bonds at the molecular ends can be easily obtained, and copolymerization with the compound (a) having both an unsaturated bond and an acid group in the molecule can be performed. From the viewpoint of ease of use, the heat reduction method is preferable.

Examples of the radical initiator used in the production of the acid-modified polyolefin (A) include organic peroxides and azo compounds.
Examples of the organic peroxide include monofunctional peroxides (those having one peroxide group in the molecule, specifically, benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.). ) And polyfunctional peroxide [those having two or more peroxide groups in the molecule, specifically 2,2-bis (4,5-di-t-butylperoxycyclohexyl) propane, di-t- Butyl peroxyhexahydroterephthalate, diallyl peroxydicarbonate, etc.] and the like.
Examples of the azo compound include azobisisobutyronitrile, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobiscyclohexane-1-carbonitrile, 2,2. '-Azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), etc. Can be mentioned.
Of these, organic peroxides are preferable from the viewpoint of copolymerizability, monofunctional peroxides are more preferable, and di-t-butyl peroxide, lauroyl peroxide and dicumylper are particularly preferable. It is an oxide.

In order to synthesize the acid-modified polyolefin (A) by the methods (1) to (3) above, the polyolefin (E1) or polyolefin (E2) is heated and mixed with the above-mentioned (a) under nitrogen aeration. Is preferable.
At this time, since the (a) may be vaporized, it is more preferable to flow hot water at a temperature at which the (a) is melted in the reflux tube to reflux the (a).
The temperature at which the above (E1) or (E2) and the above (a) are mixed is not particularly limited as long as it is equal to or higher than the melting point of the used (E1) or (E2), but is 160 ° C. or higher and 220 ° C. or lower. It is preferable that the temperature is 180 ° C. or higher and 210 ° C. or lower. When the temperature is 160 ° C. or higher, the rate of the addition reaction of (a) does not become too slow and the heating time can be shortened. When the temperature is 220 ° C. or lower, the self-polymerization of (a) can be suppressed, and the aqueous solution described later can be suppressed. It is possible to suppress deterioration of the water dispersibility of the dispersion (D) and the water resistance of the polyolefin molded product described later.
The time for mixing (E1) or (E2) with (a) is not particularly limited, but it is industrially preferable to keep it within 25 hours.
Further, when synthesizing the acid-modified polyolefin (A) by the above methods (1) to (3), if necessary, an antioxidant [hindered phenolic antioxidant [Irganox 1010 (manufactured by BASF)) ) Etc.] etc.] may be added.

Since the above-mentioned (A) produced by the above-mentioned method (3) may contain a large amount of the above-mentioned (a) which has not been reacted, even if the above-mentioned (a) is removed by a known method and used. Good. As a method for removing the above (a), a method of heating above the boiling point of the above (a) and removing the pressure under reduced pressure, and a method of dissolving the above (A) in a solvent and dissolving the above (A). Although there is no such method, there is a method of purifying the above (a) by pouring it into a soluble solvent and precipitating the above (A). Of these, from the viewpoint of manufacturing, a method of removing by reducing pressure is preferable.

The weight ratio of the total weight of the polyolefin (E1) and the polyolefin (E2) to the weight of the compound (a) in synthesizing the acid-modified polyolefin (A) by the above methods (1) to (3) [[ (E1) + (E2)] / (a)] is preferably 1000/1 to 1000/200, and more preferably 1000/11 to 1000/200, from the viewpoint of reaction efficiency.

The acid value of the acid-modified polyolefin (A) used in the present invention is preferably 1 to 12 mgKOH / g, more preferably 1 to 9 mgKOH / g, and particularly preferably 1 to 9 mgKOH / g from the viewpoint of dyeing fastness and color uniformity. Is 1 to 5.5 mgKOH / g.
The acid value of (A) changes the input amounts of (E1), (E2) and (a) and the reaction time in the production method of (A) of (1) to (3). It can be adjusted by.

The acid value of the acid-modified polyolefin (A) is measured by the following procedures (1) to (3).
(1) Dissolve 1 g of (A) as a sample in 100 g of xylene whose temperature has been adjusted to 100 ° C.
(2) Titration is performed with a 0.1 mol / L potassium hydroxide ethanol solution using phenolphthalein as an indicator.
(3) Calculate the acid value by the following formula.
Acid value (mgKOH / g) = (A × f × 0.1) / S
However, A: the number of mL of 0.1 mol / L potassium hydroxide aqueous solution required for titration,
f: Titer of 0.1 mol / L potassium hydroxide aqueous solution,
S: Sampling amount (g)
In the above measurement, one acid anhydride group is equivalent to one carboxyl group. The acid value in the examples described below was in accordance with the above method.

The number average molecular weight (Mn) of the acid-modified polyolefin (A) is preferably 1,000 or more and 200,000 or less. If it is 1,000 or more, a strong film can be formed, which is preferable from the viewpoint of adhesion to polypropylene. When it is 200,000 or less, the aqueous dispersion described later has good water dispersibility.
Further, from the viewpoint of adhesion to polypropylene and water dispersibility, it is more preferably 3,000 or more and 100,000 or less, and particularly preferably 5,000 or more and 50,000 or less.
The number average molecular weight (Mn) of the present invention is measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: High-temperature gel permeation chromatograph ["Alliance GPC V2000", manufactured by Waters Corp.]
Solvent: orthodichlorobenzene
Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm MIXED-B [manufactured by Polymer Laboratories Co., Ltd.] is connected in series. Column temperature: 135 ° C.

The melting point of the acid-modified polyolefin (A) is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and particularly preferably 90 ° C. or lower, from the viewpoint of dyeability and texture of the polyolefin molded product. .. The melting point of (A) is preferably 30 ° C. or higher, and more preferably 60 ° C. or higher.
In the present invention, the melting point means the melting peak temperature measured according to JIS K7122 (transition heat measurement method) using DSC (differential scanning calorimetry). Examples of the DSC include DSC2910 [trade name, manufactured by TA Instruments Co., Ltd.] and the like.
Since the melting point of (A) depends on the melting points of the raw materials polyolefins (E1) and (E2) used for producing the acid-modified polyolefin (A), low melting point polyolefins are used as the raw material polyolefins (E1) and (E2). It can be adjusted by a method such as selection.
Examples of the low melting point polyolefin include a copolymer of ethylene and C4 to 30 unsaturated monomers (1-butene, 2-butene, 1-hexene, etc.), and propylene and C4 to 30 unsaturated monomers (1). Copolymers with -butene, 2-butene, 1-hexene and 1,4-hexadien, etc.), unsaturated monomers of ethylene, propylene and C4-30 (1-butene, 2-butene, 1-hexene and It is selected from the group consisting of a ternary copolymer with (1,4-hexadiene, etc.) and unsaturated monomers of C4 to 30 (1-butene, 2-butene, 1-hexene, 1,4-hexadiene, etc.). Examples thereof include those obtained by polymerizing or copolymerizing at least one kind of monomer (poly-1-butene, 1-butene / 1-hexene copolymer, etc.).
Alternatively, when polyethylene or polypropylene is polymerized, it can be obtained by controlling the three-dimensional structure so as to have a low melting point with a metallocene catalyst or the like.

The amine compound (B) contained in the composition of the first invention is a compound having at least three amino groups. The amino group referred to here refers to a so-called primary amino group (-NH ₂ ), and does not include a so-called secondary amino group (-NHR ₁ ) and a tertiary amino group (-NR ₁ R _2).
The amine compound (B) having at least 3 amino groups includes melamine, triamterene, tris (2-aminoethyl) amine, 1,2,3-propanetriamine, 3,3'-diaminobenzidine and at least 3 amino groups. Examples thereof include polymers having individual compounds (polyallylamine, polyethyleneimine, aminoethylated acrylic polymer, etc.).
Of these, a polymer having at least three amino groups is preferable from the viewpoint of stainability, and polyallylamine and polyethyleneimine are more preferable.

Polyallylamine is a method of obtaining a polymer by vapor-phase polymerization of monoallylamine using tetrafluorohydrazine as a catalyst (see, for example, US Pat. No. 3,062798), in which an inorganic acid salt of monoallylamine is used as a molecule in a polar solvent. A method of polymerizing using a radical polymerization initiator containing an azo group and a cationic nitrogen (see, for example, JP-A-58-201811 and JP-A-2-14364), and in a medium containing an organic solvent. In the above, the addition salts of various allylamines can be obtained by a method of polymerizing in the presence of a radical polymerization initiator composed of a specific azo compound (see, for example, Patent No. 3570615).
Moreover, PAA [manufactured by Nittobo Medical Co., Ltd.] and the like can be mentioned as a commercially available product of polyallylamine.

Polyethyleneimine can be obtained by a known method such as ring-opening polymerization of ethyleneimine and polycondensation of ethylene chloride and ethylenediamine.
Examples of commercially available polyethyleneimine products include epomin [manufactured by Nippon Shokubai Co., Ltd.] and the like.

As a method for obtaining an aminoethylated acrylic polymer, there is a method of polymerizing a (meth) acrylic acid copolymer and then polymerizing ethyleneimine (see, for example, Japanese Patent Application Laid-Open No. 2003-192722).
Examples of commercially available aminoethylated acrylic polymers include Polyment [manufactured by Nippon Shokubai Co., Ltd.] and the like. Of these, polyallylamine having a degree of polymerization of 3 or more is preferable from the viewpoint of stainability.

When the (B) has two or less amino groups, the (B) may be an acid-modified polyolefin (A) or a dye (F) when the polyolefin base material is coated with the aqueous dispersion (D) described later. ) Etc. are insufficient, and the polyolefin molded product cannot be sufficiently surface-modified. The number of amino groups in (B) is preferably 20 or more, and more preferably 50 or more.
Further, the number of amino groups contained in (B) is preferably 1,000 or less from the viewpoint of affinity with polyolefin.

The primary amine value of (B) is preferably 250 to 1,200 mgKOH / g, more preferably 300 to 1,100 mgKOH / g, and 500 to 1,000 mgKOH / g from the viewpoint of dyeability. Is particularly preferable.

The primary amine value of (B) can be obtained by subtracting the partial amine value from the total amine value of (B), and the total amine value and the partial amine value are each measured by the following methods. ..

<Method of measuring total amine value>
(1) Weigh 1 g of the sample precisely.
(2) Add 30 ml of neutral ethanol (BCG neutral) and dissolve.
(3) Titrate with 0.2 mol / l ethanolic hydrochloric acid solution (titer: f1). [Titration: (A1) ml]
Total amine value (mgKOH / g) = 56.11 x 0.2 x (A1) x (f1)
<Method of measuring partial amine value>
(1) Weigh 1 g of the sample precisely.
(2) Add 30 ml of neutral ethanol (BCG neutral) and dissolve.
(3) Add 5 ml of a 25 wt% ethanol solution of salicylaldehyde and leave at room temperature for about 30 minutes.
(4) Titrate with 0.2 mol / l ethanolic hydrochloric acid solution (titer: f2). [Titration: (A2) ml]
Partial amine value (mgKOH / g) = 56.11 x 0.2 x (A2) x (f2)
Even when the sample is a mixture such as an aqueous solution and isolation is difficult, the concentration of (B) is analyzed using a known analytical method, and the total amine value and the partial amine value are calculated by making corrections to the above formula. be able to.

The number average molecular weight of (B) is preferably 1,000 to 70,000, more preferably 1,500 to 50,000, and 3,000 to 30,000 from the viewpoint of dyeability. Is particularly preferable.

The number average molecular weight of (B) is measured by gel permeation chromatography (GPC). The measurement conditions are as follows.
Equipment: Gel Permeation Chromatograph ["HLC-8320GPC", manufactured by Tosoh Corporation]
Solvents: Methanol / water (30% (v / v)), sodium acetate 0.5% (w / v), acetic acid 0.5% (w / v)
Sample concentration: 0.25%
Column stationary phase: TSKgel guard chromatography PWXL, TSKgel G6000PWXL, TSKgel G3000PWXL [all manufactured by Tosoh Corporation]
Column temperature: 40 ° C

The surfactant (C) used in the present invention is a group consisting of an anionic surfactant (C1), a cationic surfactant (C2), an amphoteric surfactant (C3) and a nonionic surfactant (C4). At least one surfactant selected from.
As the surfactant (C), the compounds exemplified below can be preferably used as having the effect of increasing the dispersibility in water of the above (A) and the effect of increasing the wettability to the polyolefin molded product. ..

Examples of the anionic surfactant (C1) include ether carboxylic acids (salts) having an alkyl group having 8 to 24 carbon atoms [(poly) oxyethylene (repeating units 1 to 100) sodium lauryl ether acetate, etc.] and carbon atoms. Ether sulfate ester salt having an alkyl group of 8 to 24 [(poly) oxyethylene (repetition unit number 1 to 100) sodium lauryl sulfate, etc.], sulfosuccinic acid ester salt having an alkyl group of 8 to 24 carbon atoms [mono or dialkyl Sulfosuccinic acid ester di or monosodium, (poly) oxyethylene (repetition units 1 to 100) mono or dialkyl sulfosuccinate di or monosodium, etc.], (poly) oxyethylene (repetition units 1 to 100) palm oil fatty acid monoethanol Sodium amide sulfate, sulfonates having an alkyl group of 8 to 24 carbon atoms (sodium dodecylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, etc.), phosphate ester salts having an alkyl group of 8 to 24 carbon atoms [lauryl phosphate] Sodium and (poly) oxyethylene (number of repeating units 1 to 100) sodium lauryl ether phosphate, etc.], fatty acid salts (sodium oleate, sodium laurate, triethanolamine laurate, etc.), acylated amino acid salts (palm oil fatty acids, etc.) Methyl taurine sodium and the like) and amine neutralized products of fatty acids (neutralized products of oleic acid, lauric acid or behenic acid with secondary amines or tertiary amines, etc.) and the like can be mentioned.

Examples of the cationic surfactant (C2) include quaternary ammonium salt type and amine salt type cationic surfactants.
Examples of the quaternary ammonium salt-type cationic surfactant include tertiary amines and quaternary agents (alkyl halides such as methyl chloride, methyl bromide, ethyl chloride and benzyl chloride, dimethyl sulfate, dimethyl carbonate, ethylene oxide and the like). Didecyldimethylammonium chloride, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalconium chloride), polyoxyethylenetrimethylammonium chloride, stearamide ethyldiethylmethylammonium metosulfate, etc. Can be mentioned.
As the amine salt type cationic surfactant, 1st to 3rd grade amines are used as inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid). And alkyl phosphoric acid, etc.) can be used.
Specific examples of amine salt-type cationic surfactants include inorganic or organic acid salts of higher amines (aliphatic amines having 8 to 24 carbon atoms: laurylamine, stearylamine, hardened beef amine, rosinamine, etc.); lower amines. Higher fatty acids (fatty acids with 8 to 24 carbon atoms: stearic acid, oleic acid, etc.) salts (amines having 1 to 7 carbon atoms); and inorganic or organic acid salts such as ethylene oxide adducts of aliphatic amines. Can be mentioned.

Examples of the amphoteric surfactant (C3) include carboxybetaine type amphoteric surfactants [fatty acid amide propyldimethylaminoacetic acid betaine having 10 to 18 carbon atoms (palm oil fatty acid amide propyl betaine, etc.), alkyl (carbon number 10 to 18) dimethyl. Betaine aminoacetate (betaine lauryldimethylaminoacetate, etc.), imidazolinium-type carboxybetaine (2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, etc.)], sulfobetaine-type amphoteric surfactant [carbon number 10 to 18 fatty acids amidopropyl hydroxyethyl sulfobetaine (palm oil fatty acid amide propyl dimethyl hydroxyethyl sulfobetaine, etc.) and dimethylalkyl (10 to 18 carbon atoms) dimethyl hydroxyethyl sulfobetaine (lauryl hydroxy sulfobetaine, etc.)] and amino acids Examples thereof include type amphoteric surfactants (such as sodium β-laurylaminopropionate).

Examples of the nonionic surfactant (C4) include an alkylene oxide (hereinafter abbreviated as AO) addition type nonionic surfactant and a polyhydric alcohol type nonionic surfactant.
As the AO adduct type nonionic surfactant, the AO (2 to 4 carbon atoms, preferably 2) adduct (1 to 30 adducts per active hydrogen) of the higher alcohol (8 to 32 carbon atoms) ), Alcohol (1 to 12 carbon atoms) phenol adduct (hereinafter abbreviated as EO) adduct (additional moles 1 to 30), styrrified phenol EO adduct (additional moles 1 to 30), higher amine (8 to 22 carbon atoms) AO (2 to 4 carbon atoms, preferably 2) adduct (1 to 40 moles added per active hydrogen), EO adduct of fatty acid (8 to 18 carbon atoms) (Additional moles 1 to 60 per active hydrogen), EO adduct of polypropylene glycol (number average molecular weight = 200 to 4,000) (additional moles 1 to 50 per active hydrogen), polyoxyethylene (Number of repeating units 3 to 30) Alkyl (6 to 20 carbon atoms) EO adduct of allyl ether and sorbitan monolaurate (1 to 30 addition moles per active hydrogen) and EO adduct of sorbitan monooleate (1 to 30 additions) Polyhydric (2-8 valent or higher) alcohols (2-30 carbon atoms) fatty acids (8-24 carbon atoms) ester EO adducts (active hydrogen) such as 1 to 30 moles added per active hydrogen The number of added moles per piece 1 to 30) and the like can be mentioned.
Examples of the polyhydric alcohol type nonionic surfactant include fatty acids (carbons) of polyhydric (2-8 valent or higher) alcohols (2 to 30 carbon atoms) such as glycerin monoolate, sorbitan monolaurate and sorbitan monoolate. Numbers 8 to 24) Esters and fatty acids (10 to 18 carbon atoms) alkanolamides such as lauric acid monoethanolamide and lauric acid diethanolamide can be mentioned.

Of the above (C1) to (C4), anionic surfactants (C1) and nonionic surfactants (C4) are preferable from the viewpoint of leveling property, and fatty acid salts and carbons are more preferable. AO (2-4 carbon atoms, preferably 2) adducts of surfactants having alkyl groups of 8 to 24 and higher alcohols (8 to 32 carbon atoms) (additional moles 1 to 1 per active hydrogen) 30), and particularly preferable is an EO adduct of a higher alcohol (8 to 22 carbon atoms) (4 to 13 added moles per active hydrogen).

The composition of the present invention preferably further contains water and is an aqueous dispersion (D) from the viewpoint of being used in the coating agent of the present invention described in detail later. The aqueous dispersion (D) may further contain an organic solvent (methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, toluene, xylene, etc.).

The composition of the first invention is a cross-linking agent that crosslinks (A), (B), (C), etc. in addition to the above-mentioned (A), (B), (C), water and an organic solvent. It may contain a plasticizer for adjusting the physical properties of the coating film with the following coating agent, a crystal nucleating agent for adjusting the formability of the coating film with the following coating agent, and the like.

Examples of the cross-linking agent include isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds and silane coupling agents.
Of these, a cross-linking agent having one or more functional groups selected from the group consisting of a carbodiimide group, an epoxy group, an isocyanate group and a blocked isocyanate group is more preferable.

Among the above-mentioned cross-linking agents, preferable cross-linking agents used for cross-linking (A) and (B) include the cross-linking agent (x) described in detail below.
The cross-linking agent (x) is a compound that satisfies at least one of the following (i) to (ii).
(I)
The cross-linking agent (x) has at least two groups selected from the group consisting of an epoxy group, an isocyanate group and a blocked isocyanate group in one molecule.
(Ii)
Crosslinker (x) has at least one carbodiimide group in one molecule.

Examples of the cross-linking agent (x) include aliphatic epoxy resins (ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and water. Additive bisphenol A diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.), aromatic epoxy resin (resorcinol diglycidyl ether, bisglycidyl terephthalate, diglycidyl phthalate, bisphenol A diglycidyl ether, etc.), isocyanate compounds (Hexamethylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, toluenediisocyanate, isophorone diisocyanate, etc.) and those blocked with a blocking agent, carbodiimide [polycarbodiimide resin manufactured by Nisshinbo Chemical Co., Ltd. and cyclic carbodiimide manufactured by Teijin Co., Ltd. It can be obtained from the market as such.]

Examples of the plasticizer include hydrocarbons (liquid paraffin, paraffin wax, etc.), esters (dibutylhexyl phthalate, dibutyl phthalate, etc.), and higher alcohols [alcohols having 8 to 22 carbon atoms (oleyl alcohol and stearyl). Alcohol, etc.)], etc.
Of these, higher alcohols are preferable from the viewpoint of affinity with polyolefin.

Examples of the crystal nucleating agent include dibenzylideneacetones, sodium benzoate, potassium 1,2-hydroxystearate, magnesium benzoate, and amide compounds (N, N'-dicyclohexyl-2,6-naphthalenedicarboxamide, etc.). And quinacridone compounds and the like.

The weight ratio (A / B) of the (A) to the (B) contained in the composition of the first invention is preferably 5/95 to 95/5, and is preferably 50/50 to 95/5. It is more preferably 55/45 to 90/10, and most preferably 60/40 to 80/20.
By setting the amount of (A) in this range, the force of adhesion on the polyolefin molded product is improved, and the dyeability and dyeing fastness are also improved.
Further, by setting the amount of (B) in this range, the ability to adsorb the dye (F) described later is improved, and the dyeability is also improved.

The composition of the first invention preferably contains the surfactant (C) in an amount of 0.1 to 200% by weight based on the weight of the above (A).
When the content of (C) is 0.1% by weight or more based on the weight of (A), when the composition of the first invention is the aqueous dispersion (D), ( Since D) can be prevented from being repelled by the polyolefin substrate, excellent dyeability can be imparted.
Further, when the content of the (C) is 200% by weight or less based on the weight of the (A), the adhesion to the polyolefin molded product is improved and the washing fastness is improved.
Further, from the viewpoint of color uniformity and the like, it is more preferable to contain the above (C) in an amount of 0.1 to 50% by weight, particularly preferably 5 to 30% by weight, based on the weight of the above (A). ..

When the composition of the present invention is contained in water to form an aqueous dispersion (D) for use in the coating agent of the present invention described in detail later, the ratio of the total weight of water and the organic solvent is the ratio of the working efficiency. From the viewpoint, it is preferably 20 to 99% by weight based on the weight of (D).

The weight ratio of the cross-linking agent is 0.1 to 10% by weight based on the weight of the acid-modified polyolefin (A) from the viewpoint of adhesion to the polyolefin molded product and water resistance of the polyolefin molded product. preferable.
The weight ratio of the plasticizer is preferably 0.1 to 10% by weight based on the weight of the acid-modified polyolefin (A) from the viewpoint of adhesion to the polyolefin molded product.
From the viewpoint of water resistance of the polyolefin molded product, the weight ratio of the crystal nucleating agent is preferably 0.01 to 10% by weight based on the weight of the acid-modified polyolefin (A).

The composition of the first invention can be obtained as an aqueous dispersion (D) by, for example, mixing the above (A), (B), (C) and water. The method of mixing the (A), (B), (C) and water is not particularly limited, but a method of mixing the (B) after making the (A) and the (C) an aqueous dispersion is produced. It is preferable from the above viewpoint.

The method for preparing the aqueous dispersions of (A) and (C) is as follows.
(1) The above (A), (C) and amine (H) (primary amine having two or less amino groups, secondary amine, tertiary amine, etc.) are mixed in a solvent, and water is added thereto. Is added little by little to invert the phase, and then the solvent is removed (phase inversion emulsification method);
(2) A method in which the (A), (C), amine (H) and water are placed in a pressure-resistant container, heated to a temperature equal to or higher than the melting point of (A), and dispersed by stirring (forced emulsification method).
And so on.

The amine (H) is an amine used to neutralize the acid group of (A) so that the (A) can be easily dispersed in water.
Examples of the primary amine having two or less amino groups include compounds having 1 to 8 carbon atoms, and specific examples thereof include aniline, hexylamine, and octylamine.
Examples of the secondary amine having two or less amino groups include compounds having 1 to 8 carbon atoms, and specific examples thereof include methylethanolamine, diethanolamine, and morpholine.
Examples of the tertiary amine having two or less amino groups include compounds having 1 to 8 carbon atoms, and specific examples thereof include triethylamine, methyldiethanolamine, and dimethylaminoethanol.
The above (H) is preferably a secondary amine and a tertiary amine, and more preferably a tertiary amine from the viewpoint of suppressing an unexpected reaction with the above (A) and the like.
The weight ratio of (H) is preferably 0.1 to 50% by weight based on the weight of (A).

Further, the composition of the first invention, which does not contain water, can be obtained, for example, by heating the aqueous dispersion (D) and evaporating the water.

The first composition of the present invention, particularly the aqueous dispersion (D), can be used for paints, adhesives, coating agents, fiber treatment agents and the like. Among them, paints used for polyolefin base materials (automotive interior paints and bumper primers, etc.), adhesives used for bonding polyolefins to polar materials (PP / aluminum adhesives, etc.), and hydrophilicity added to the surface of polyolefins. Coating agent (antistatic agent, antifogging agent, antifouling agent, etc.) and fiber treatment agent (cellulose nanofiber / PP composite material sizing agent) for imparting polarity and polyolefin adhesion to the fiber surface. It is suitably used as a sizing agent for carbon fibers / PP composite materials, a sizing agent for glass fibers / PP composite materials, a dyeing agent for PP fibers / cloth, etc.). In particular, it is useful as a stain-imparting agent.

The coating agent of the present invention is a coating agent containing the first composition, and is particularly preferably a coating agent containing the aqueous dispersion (D).
Further, the coating agent may contain a pigment and a resin other than the above (A) and (B) in addition to the first composition.

Examples of pigments include inorganic pigments and organic pigments.
Examples of the inorganic pigment include titanium oxide and carbon black.
Examples of the organic pigment include azo pigments (azolake type, monoazo type, etc.) and polycyclic pigments (benzimidazolone type, phthalocyanine type, etc.) and the like.

Examples of resins other than the above (A) and (B) include polyurethane, acrylic resin, epoxy resin, melamine resin, polyamide, polyimide, polyether, polyester and polystyrene.

The higher the ratio of the total weight of the above (A), (B) and (C) contained in the coating agent, the larger the film thickness of the coating film formed by the coating agent, and therefore the harder the texture. It tends to be. When the coating agent is used for applications where texture is important (such as clothing applications), the ratio of the total weight of the above (A), (B) and (C) contained in the coating agent is the above. It is preferably 10% by weight or less, more preferably 8% by weight or less, and particularly preferably 6% by weight or less based on the weight of the coating agent.
The ratio of the total weight of (A), (B) and (C) contained in the coating agent is 0.1 based on the weight of the coating agent from the viewpoint of dyeability and dyeing fastness. The weight is preferably 1% by weight or more, and more preferably 1% by weight or more.
The ratio of the total weight of (A), (B) and (C) contained in the coating agent can be adjusted by diluting with water.

The weight ratio of the pigment contained in the coating agent of the present invention is preferably 0.01 to 10% by weight based on the weight of the coating agent from the viewpoint of dyeing fastness.
Further, the weight ratio of the resins other than the above (A) and (B) contained in the coating agent of the present invention is 0.01 to 0.01 based on the weight of the coating agent from the viewpoint of adhesion to the polyolefin base material. It is preferably 30% by weight.

The polyolefin molded product of the present invention is a polyolefin molded product containing the composition of the first invention, and examples thereof include a polyolefin molded product having a coating film with the coating agent on the surface of the polyolefin base material. The polyolefin molded product having the coating film with the coating agent has a coating film containing the composition of the first invention.
Examples of the polyolefin base material include processing of polyolefin into lumps (plates, rods, spheres, etc.), sheets, films, threads and cloths (woven fabrics, knitted fabrics, non-woven fabrics, etc.). Among the above-mentioned polyolefin substrates, films and cloths are preferable from the viewpoint of production.

A coating film can be formed on the surface of the polyolefin molded product by coating the surface of the polyolefin base material with the above-mentioned coating agent and then heat-treating to remove water and the like. Examples of the coating method include a method of immersing the polyolefin base material in the coating agent, a method of spraying the coating agent on the surface of the base material, a method of applying using a known coating device, and the like.
The temperature of the heat treatment is preferably less than the softening point of the polyolefin base material and higher than the melting point of the acid-modified polyolefin (A).

The larger the amount of the coating agent used, the larger the film thickness of the coating film of the polyolefin molded product, and the harder the texture tends to be. When the coating agent is used for applications where texture is important (such as clothing applications), it is preferable that the amount used is small.
The weight ratio of the coating film is preferably 10% by weight or less based on the weight of the polyolefin molded product having the coating film, from the viewpoint of facilitating the imparting of dyeability without deteriorating the texture. It is more preferably 7% by weight or less, and particularly preferably 6% by weight or less.
The weight ratio of the coating film is preferably 0.1% by weight or more based on the weight of the polyolefin molded product having the coating film, and is preferably 1% by weight or more, from the viewpoint of exerting the function as a coating agent. Is more preferable.

The polyolefin molded product of the present invention may further contain a dye (F), and the coating film may further contain a dye (F).
As the dye (F), a commercially available known dye or the like can be used. Specific examples thereof include reactive dyes, acidic dyes, cationic dyes, disperse dyes, direct dyes, mordant dyes, acidic mordant dyes, naphthol dyes and bat dyes. Of these, from the viewpoint of dyeability, reactive dyes, acid dyes, acid mordant dyes and naphthol dyes are preferable, and reactive dyes and acid dyes are more preferable.
As a means for producing the polyolefin molded product containing the dye (F), after producing the polyolefin molded product containing the composition of the present invention (for example, the coating on the surface of the polyolefin base material by the above method). A method of immersing the agent in an aqueous solution containing the dye (F) after coating the agent to form a coating film can be mentioned.
Regarding the aqueous solution containing the dye (F), the weight ratio of the dye (F) is 0.01 to 5% by weight based on the weight of the aqueous solution containing the dye (F) from the viewpoint of dyeing fastness. It is preferable to have.
The temperature of the aqueous solution containing the dye (F) is preferably 30 to 120 ° C. from the viewpoint of dyeability.
Further, the time for immersing in the aqueous solution containing the dye (F) is preferably 10 to 300 minutes from the viewpoint of dyeability.

Next, the composition which is the second invention of this invention will be described.
The composition according to the second invention is a condensate (AB) of an acid-modified polyolefin (A) and an amine compound (B) having at least three amino groups, an anionic surfactant (C1), and a cationic surfactant. It is a composition containing at least one surfactant (C) selected from the group consisting of a surfactant (C2), an amphoteric surfactant (C3) and a nonionic surfactant (C4).

Examples of the above (A), (B) and (C) used in the second invention include compounds similar to those exemplified as (A), (B) and (C) in the first invention. The same applies to preferable ones.
Further, the composition of the second invention may contain a plasticizer, a crystal nucleating agent and the like as in the first invention.

Further, when the composition of the second invention is used for a coating agent described later, it may be an aqueous dispersion containing water as in the first invention (the aqueous dispersion is further an organic solvent). May be contained).
Further, the composition of the second invention may be a mixed solution containing an organic solvent.
Examples of the organic solvent include alcohols (methanol, ethanol, isopropanol, butanol, octanol, etc.);
Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.);
Esters (ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.);
Ether (tetrahydrofuran, tetrahydropyran, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, etc.);
Aromatic hydrocarbons (benzene, toluene, xylene, etc.);
Amides (dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.)
And so on.
The above-mentioned organic solvent may be used alone or in combination of two or more.

When the composition of the second invention is an aqueous dispersion containing water or a mixed solution containing an organic solvent, the ratio of the total weight of the water and the organic solvent is determined from the viewpoint of work efficiency. It is preferably 20 to 99% by weight based on the weight of the aqueous dispersion or the mixed solution.

As described above, the condensate (AB) is a condensate of the acid-modified polyolefin (A) and an amine compound (B) having at least three amino groups, and is described in detail later. The composition according to the first invention can be obtained by a method such as heating at 60 to 200 ° C.

In the second invention, the weight ratio (A / B) of the above (A) used for the synthesis of the condensate (AB) and the above (B) used for the synthesis of the condensate (AB) is. It is preferably 5/95 to 95/5.
By setting the amount of (A) in this range, the force of adhesion on the polyolefin molded product is improved, and the dyeability and dyeing fastness are also improved.
Further, by setting the amount of (B) in this range, the ability to adsorb the dye (F) is improved, and the dyeability is also improved.
Further, the weight ratio (A / B) of the above (A) used for the synthesis of the condensate (AB) and the above (B) used for the synthesis of the condensate (AB) is the dyeability and the dyeability. From the viewpoint of dyeing fastness, it is more preferably 50/50 to 95/5, particularly preferably 55/45 to 90/10, and most preferably 60/40 to 80/20.

In the second invention, the content of the (C) contained in the composition of the second invention is 0, based on the weight of the (A) used for the synthesis of the condensate (AB). It is preferably 1 to 200% by weight.
When the content of (C) is 0.1% by weight or more based on the weight of (A), when the composition of the second invention is the aqueous dispersion, the aqueous dispersion Since the body can be prevented from being repelled by the polyrefin base material, excellent dyeability can be imparted.
Further, when the content of (C) is 200% by weight or less based on the weight of (A), the adhesion to the polyolefin molded product is improved and the washing fastness is improved.
From the viewpoint of color uniformity and the like, it is more preferable to contain the above (C) in an amount of 0.1 to 100% by weight based on the weight of the above (A), and more preferably 0.1 to 50% by weight. It is particularly preferable, and it is most preferable to contain 5 to 30% by weight.

The composition of the second invention can be obtained by a method such as heating the composition of the first invention at 60 to 200 ° C.
The heating of the composition according to the first invention can be carried out by the following methods [1] to [3] and the like.
[1] The composition itself, which is the first invention, is heated.
[2] The coating agent containing the composition according to the first invention is heated.
[3] The surface of the polyolefin base material is coated with a coating agent containing the composition according to the first invention, and then heated.

When carried out by the methods of [1] and [2], an aqueous dispersion or a mixed solution can be obtained by adding and mixing the above-mentioned water and / or organic solvent after heating. At this time, the above-mentioned (C) may be further added.

When the method of [3] is carried out, the temperature of the heat treatment is set to 60 in the step of producing the coating film and the polyolefin molded product using the composition of the first invention described in the description of the first invention. It can be carried out at ~ 200 ° C., and can be obtained as a polyolefin molded product having a coating film containing the composition of the second invention of the present invention.

The aqueous dispersion containing the composition of the second invention or the mixed solution of the composition of the second invention and the organic solvent is coated in the same manner as the aqueous dispersion of the first invention (same for the preferred embodiment). The coating agent and the polyolefin molded product of the present invention can be produced by using this coating agent as an agent.
Further, in the calculation of the preferable weight ratio, the weight of the condensate (AB) used for the synthesis of the condensate (AB) is used instead of the weight of the above (A), and the weights of the above (A) and (B) are used. ) And (C), the total weight of (A), (B), (C) and (AB) may be used instead of the total weight of (A) and (C).

Next, the composition which is the third invention of this invention will be described.
The composition according to the third invention comprises a compound (AxB), an anionic surfactant (C1), a cationic surfactant (C2), an amphoteric surfactant (C3) and a nonionic surfactant (C4). A composition containing at least one surfactant (C) selected from the group consisting of).
The compound (AxB) is a compound obtained by cross-linking an acid-modified polyolefin (A) and an amine compound (B) having at least three amino groups with a cross-linking agent (x).
The cross-linking agent (x) is a composition that satisfies at least one of the following (i) to (ii).
(I)
The cross-linking agent (x) has at least two groups selected from the group consisting of an epoxy group, an isocyanate group and a blocked isocyanate group in one molecule.
(Ii)
Crosslinker (x) has at least one carbodiimide group in one molecule.

The (A), (B), (C) and (x) used in the third invention are exemplified as (A), (B), (C) and (x) in the first invention. The same compounds as those of the above are mentioned, and the preferred ones are also the same.
Further, the composition of the third invention may contain a plasticizer, a crystal nucleating agent and the like as in the first invention.

Further, when the composition according to the third invention is used as a coating agent described later, it may be dispersed in water to be an aqueous dispersion as in the second invention (the aqueous dispersion is further described as an aqueous dispersion). It may contain an organic solvent), or it may be a mixed solution with an organic solvent.
When the composition according to the third invention is an aqueous dispersion containing water or a mixed solution containing an organic solvent, the ratio of the total weight of the water and the organic solvent is determined from the viewpoint of work efficiency. It is preferably 20 to 99% by weight based on the weight of the aqueous dispersion or the mixed solution.

As described above, the compound (AxB) is a compound obtained by cross-linking an acid-modified polyolefin (A) and an amine compound (B) having at least three amino groups with a cross-linking agent (x), and later. As will be described in detail, the composition according to the first invention, which contains the cross-linking agent (x), can be obtained by heating at 60 to 200 ° C. or the like.

The number average molecular weight (Mn) of the compound (AxB) is preferably 5,000 to 500,000 from the viewpoint of dyeability and dye fastness.
The number average molecular weight (Mn) of the compound (AxB) can be measured by GPC under the following conditions.
Equipment: High-temperature gel permeation chromatograph ["Alliance GPC V2000", manufactured by Waters Corp.]
Solvent: orthodichlorobenzene
Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm MIXED-B [manufactured by Polymer Laboratories Co., Ltd.] is connected in series. Column temperature: 135 ° C.

In the third invention, the weight ratio (A / B) of the (A) used for the synthesis of the compound (AxB) and the (B) used for the synthesis of the compound (AxB) is 5 /. It is preferably 95 to 95/5.
By setting the amount of (A) in this range, the force of adhesion on the polyolefin molded product is improved, and the dyeability and dyeing fastness are also improved.
Further, by setting the amount of (B) in this range, the ability to adsorb the dye (F) is improved, and the dyeability is also improved.
Further, the weight ratio (A / B) of the above (A) used for the synthesis of the compound (AxB) and the above (B) used for the synthesis of the compound (AxB) is dyeability and dye fastness. From the viewpoint of degree, it is more preferably 50/50 to 95/5, particularly preferably 55/45 to 90/10, and most preferably 60/40 to 80/20.

In the third invention, the content of the (C) contained in the composition is 0.1 to 200% by weight based on the weight of the (A) used for the synthesis of the compound (AxB). It is preferably a certain composition.
When the content of (C) is 0.1% by weight or more based on the weight of (A), the aqueous dispersion is the aqueous dispersion when the composition of the third invention is the aqueous dispersion. Can be prevented from being repelled by the polyrefin base material, so that excellent dyeability can be imparted.
Further, when the content of (C) is 200% by weight or less based on the weight of (A), the adhesion to the polyolefin molded product is improved and the washing fastness is improved.
From the viewpoint of color uniformity and the like, it is more preferable to contain the above (C) in an amount of 0.1 to 100% by weight based on the weight of the above (A), and more preferably 0.1 to 50% by weight. It is particularly preferable, and it is most preferable to contain 5 to 30% by weight.

The weight ratio of the cross-linking agent (x) used for the synthesis of the compound (AxB) is 0.1 based on the total weight of the above-mentioned (A) and (B) from the viewpoint of dyeability and dye fastness. It is preferably ~ 50% by weight.

The composition of the third invention is the composition of the first invention, and can be obtained by a method such as heating the composition containing the cross-linking agent (x) at 60 to 200 ° C.
The heating of the composition containing the cross-linking agent (x) can be carried out by the following methods [1] to [3] and the like.
[1] The composition itself, which is the first invention, is heated.
[2] The coating agent containing the composition according to the first invention is heated.
[3] The surface of the polyolefin base material is coated with a coating agent containing the composition according to the first invention, and then heated.

When carried out by the methods of [1] and [2], an aqueous dispersion or a mixed solution can be obtained by adding and mixing the above-mentioned water and / or organic solvent after heating. At this time, the above-mentioned (C) may be further added.

When carried out by the method of [3], in the step of producing a coating film and a polyolefin molded product using the composition of the first invention described in the description of the first invention, the composition of the first invention A coating film containing the composition of the third invention of the present invention, which can be carried out by using the composition containing the cross-linking agent (x) as a product and setting the temperature of the heat treatment to 60 to 200 ° C. It can be obtained as a polyolefin molded product.

The aqueous dispersion containing the composition of the third invention or the mixed solution of the composition of the third invention and the organic solvent is coated in the same manner as the aqueous dispersion of the first invention (same for the preferred embodiment). The coating agent and the polyolefin molded product of the present invention can be produced by using this coating agent as an agent.
Further, in the calculation of the preferable weight ratio, the weight of the compound (AxB) used for the synthesis of the compound (AxB) is used instead of the weight of the compound (A), and the weights of the above (A) and (B) are used. And (C) may be replaced with the total weight of (A), (B), (C), (AB) and (AxB).

Further, as the polyolefin molded product of the present invention, in addition to the above-mentioned production method, the composition of the second invention and / or the composition of the third invention (if necessary, a mixture with other polyolefins) is known. Melt spinning by method [Osamu Ishizuka: Journal of the Textile Society, Vol. 18, Vol. 18 (1962) No. 3, p. It can be manufactured by the method described in 189-193].
Examples of other polyolefins include compounds exemplified as polyolefin (E1) and polyolefin (E2) in the first invention.
Further, as described above, in the method of melt-spinning the composition of the second invention and / or the composition of the third invention by a known method, the composition of the first invention is used as a raw material for melt-spinning. [Or the composition of the first invention containing the cross-linking agent (x)] may be used and heated in the process of melt spinning to obtain the composition of the second invention (or the composition of the third invention).

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates a weight% and a part indicates a weight part. In the following, Examples 16, 41, 48, and 50 will be read as Reference Examples 1 to 4, respectively.
The acid-modified polyolefins (A-1) to (A-6), amine compounds (B-1) to (B-5) and (B'-1) to (B'-) produced in Production Examples 6 to 11 The number average molecular weight (Mn) of 2) was measured by GPC under the above conditions.
The number average molecular weight (Mn) of the composition (Y-2) produced in Example 17 and the composition (Y-3) produced in Example 18 was measured by GPC under the following conditions.
Equipment: High-temperature gel permeation chromatograph ["Alliance GPC V2000", manufactured by Waters Corp.]
Solvent: Ortodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm MIXED-B [manufactured by Polymer Laboratories Co., Ltd.] is connected in series. Column temperature: 135 ° C.

Further, for the following polyolefins (E2-1) to (E2-5), ¹ H-NMR analysis for calculating the number of double bonds in the molecule per 1,000 carbons was carried out under the following conditions. ..
Equipment: Bruker AVANCE III HD400 [Frequency: 400MHz, manufactured by BRUKER Co., Ltd.]
Sample temperature: 80 ° C. when the sample is (E2-4) and (E2-5), 25 ° C. when the sample is other than (E2-4) and (E2-5).
Sample concentration: 30 mg / 0.6 ml
Reference substance: Tetramethylsilane (TMS)
Number of integrations: 16 times Deuterated solvent: Deuterated toluene when the sample is (E2-4) and (E2-5), deuterated chloroform when the sample is other than (E2-4) and (E2-5)

The acid value and melting point of the acid-modified polyolefins (A-1) to (A-6) produced in Production Examples 6 to 11 were measured by the above method.
The primary amine values of the amine compounds (B-1) to (B-5) and (B'-1) to (B'-2) were measured by the above method, and the amino groups of each amine compound were measured. The number was calculated from the primary amine value and Mn.

Production Example 1 [Production of Polyolefin (E2-1) by Thermal Decomposition Method]
100 parts of polyolefin (E1-1) [trade name "Toughmer XM5070", manufactured by Mitsui Kagaku Co., Ltd.] containing propylene and 1-butene as constituent units was charged into the reaction vessel, and while nitrogen was aerated through the gas phase part, It was heated and melted with a mantle heater and heat-decomposed at 330 ° C. for 80 minutes with stirring to obtain a polyolefin (E2-1). In (E2-1), the number of C = C bonds in the molecule per 1,000 carbons was 1.1.

Production Example 2 [Production of Polyolefin (E2-2) by Thermal Decomposition Method]
In Production Example 1, instead of (E1-1), a polyolefin (E1-2) containing propylene and 1-butene as constituent units [trade name "Toughmer XM5080", manufactured by Mitsui Chemicals, Inc.] is used for heat reduction. Polyolefin (E2-2) was obtained in the same manner as in Production Example 1 except that the conditions were set to 330 ° C. and 45 minutes. In (E2-2), the number of C = C bonds in the molecule per 1,000 carbons was 0.7.

Production Example 3 [Production of Polyolefin (E2-3) by Thermal Decomposition Method]
In Production Example 1, instead of (E1-1), a polyolefin (E1-2) containing propylene and 1-butene as constituent units [trade name "Toughmer XM5080", manufactured by Mitsui Chemicals, Inc.] is used for heat reduction. Polyolefin (E2-3) was obtained in the same manner as in Production Example 1 except that the conditions were 350 ° C. and 40 minutes. In (E2-3), the number of C = C bonds in the molecule per 1,000 carbons was 1.7.

Production Example 4 [Production of Polyolefin (E2-4) by Thermal Decomposition Method]
In Production Example 1, instead of (E1-1), a polyolefin (E1-3) containing ethylene, propylene, and 1-butene as constituent units [trade name "VESTOPLAST750", manufactured by Evonik] was used, and the heat reduction conditions were set. Polyolefin (E2-4) was obtained in the same manner as in Production Example 1 except that the temperature was 350 ° C. for 50 minutes. In (E2-4), the number of C = C bonds in the molecule per 1,000 carbons was 10.3.

Production Example 5 [Production of Polyolefin (E2-5) by Thermal Decomposition Method]
In Production Example 1, a polyolefin (E1-4) [trade name "Versify 3000", manufactured by Dow Chemical Co., Ltd.] containing ethylene and propylene as constituent units was used instead of (E1-1), and the heat reduction time was set. Polyolefin (E2-5) was obtained in the same manner as in Production Example 1 except that the time was 60 minutes. In (E2-5), the number of C = C bonds in the molecule per 1,000 carbons was 0.9.

Production Example 6 [Production of Acid-Modified Polyolefin (A-1)]
1,000 parts of (E2-1) obtained in Production Example 1 and 1 part of IRGANOX 1010 [manufactured by BASF Japan Ltd.] were added to a reactor equipped with a nitrogen vent and a reflux tube through which hot water of 80 ° C was flowed. Was added, and the inside of the kiln was replaced with nitrogen. The temperature was raised to 160 ° C. with stirring under nitrogen aeration. 46.2 parts of maleic anhydride was charged, and the temperature was raised to 200 ° C. with a slight flow of nitrogen. After stirring at 200 ° C. for 15 hours, decompression topping was performed for 5 hours to remove unreacted maleic anhydride. After cooling to 160 ° C., it was taken out from the reactor to obtain an acid-modified polyolefin (A-1). (A-1) was Mn 20,000 and the acid value was 5.0 mgKOH / g.

Production Example 7 [Production of Acid-Modified Polyolefin (A-2)]
In Production Example 6, (E2-2) was used instead of (E2-1), and the same procedure as in Production Example 6 was carried out except that the charged weight of maleic anhydride was changed to 29.4 parts, and the acid-modified polyolefin (A) was used. -2) was obtained. (A-2) was Mn 40,000 and the acid value was 1.0 mgKOH / g.

Production Example 8 [Production of Acid-Modified Polyolefin (A-3)]
In Production Example 6, the same procedure as in Production Example 6 was carried out except that (E2-3) was used instead of (E2-1) to obtain an acid-modified polyolefin (A-3). (A-3) was Mn 8,000 and the acid value was 12.0 mgKOH / g.

Production Example 9 [Production of Acid-Modified Polyolefin (A-4)]
After charging 1,000 parts of (E2-1) to the reaction apparatus and melting the mixture under a nitrogen atmosphere, 28 parts of maleic anhydride was charged under stirring while keeping the inside of the apparatus at 180 ° C. over 2 hours. Then, 5.5 parts of perbutyl D (di-t-butyl peroxide, manufactured by NOF CORPORATION) was added as a radical reaction initiator over 2 hours, and the reaction was carried out for 1 hour. After cooling to 160 ° C., the contents were taken out to obtain an acid-modified polyolefin (A-4). (A-4) had Mn 25,000 and an acid value of 15.0 mgKOH / g.

Production Example 10 [Production of Acid-Modified Polyolefin (A-5)]
In Production Example 6, (E2-4) was used instead of (E2-1), and the same procedure as in Production Example 6 was carried out except that the charged weight of maleic anhydride was changed to 10 parts, and the acid-modified polyolefin (A-5) was used. ) Was obtained. (A-5) was Mn 3,000 and the acid value was 5.0 mgKOH / g.

Production Example 11 [Production of Acid-Modified Polyolefin (A-6)]
In Production Example 6, the same procedure as in Production Example 6 was carried out except that (E2-5) was used instead of (E2-1) to obtain an acid-modified polyolefin (A-6). (A-6) was Mn 20,000 and the acid value was 5.0 mgKOH / g.

Production Example 12 [Manufacture of polyolefin non-woven fabric (PG)]
Commercially available polypropylene [trade name "SunAllomer PL500A", manufactured by SunAllomer Ltd.] was melted at 230 ° C. and discharged from a spinning nozzle whose temperature was adjusted to 230 ° C. for melt spinning. This was heated from a cooling device at 35 ° C. and 65% R. H. The cooling air was blown to cool the yarn, and the yarn was traction-thinned and stretched at a spinning speed of 4,500 m / min by a thread traction air jet device. Subsequently, the discharged threads were opened using a suction device to obtain lumpy fibers on the mobile deposition device.
Next, the massive fibers were partially thermocompression bonded using an embossing device heated to 150 ° C. to obtain a polyolefin resin non-woven fabric (PG) having a ^{fiber diameter of 2.5 dtex and a grain size of 40 g / m 2.}

Example 1 [Production of Aqueous Dispersion (D-1)]
100 parts of (A-1), 1.5 parts of dimethylaminoethanol [manufactured by Tokyo Chemical Industry Co., Ltd.], EO adduct of higher alcohol (C-1) in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. ) [Product name "Emulmin 50", manufactured by Sanyo Kasei Kogyo Co., Ltd.] 21.4 parts and 80 parts of tetrahydrofuran were charged, and the temperature was adjusted to 60 ° C. under stirring to uniformly dissolve the mixture. 233 parts of water was added little by little over 5 hours to carry out phase inversion emulsification.
After cooling to room temperature, tetrahydrofuran is removed under reduced pressure, and then an aqueous solution containing polyallylamine (B-1) [trade name "PAA-15C", concentration 15% of (B-1), Nittobo Medical (B-1) is added while stirring. Manufactured by Co., Ltd.] 285.7 parts were added to homogenize, and water was added so that the solid content was 25.0% to obtain an aqueous dispersion (D-1).

Example 2 [Production of Aqueous Dispersion (D-2)]
In Example 1, (A-2) was used instead of (A-1), and the same procedure as in Example 1 was carried out except that the charged weight of (C-1) was changed to 35.7 parts. (D-2) was obtained.

Example 3 [Production of Aqueous Dispersion (D-3)]
In Example 1, (A-3) was used instead of (A-1), and the same procedure as in Example 1 was carried out except that the charged weight of (C-1) was changed to 0.1 part. (D-3) was obtained.

Example 4 [Production of Aqueous Dispersion (D-4)]
In Example 1, (A-4) was used instead of (A-1), and the charged weight of dimethylaminoethanol was changed to 3.8 parts and the charged weight of (C-1) was changed to 7.1 parts. Aqueous dispersion (D-4) was obtained in the same manner as in Example 1 except for the above.

Example 5 [Production of Aqueous Dispersion (D-5)]
In Example 1, an aqueous dispersion (D-5) was obtained in the same manner as in Example 1 except that (A-5) was used instead of (A-1).

Example 6 [Production of Aqueous Dispersion (D-6)]
In a stainless steel autoclave equipped with a stirrer and a temperature control device, 100 parts of (A-6), 21.4 parts of (C-1), 1.5 parts of dimethylaminoethanol, and 233 parts of water were charged, and nitrogen substitution was performed by 2. I went there times. After reducing the pressure to 0.1 MPa, the temperature was raised to 160 ° C. over 30 minutes. After stirring at 1000 rpm for 3 hours, the mixture was cooled to room temperature.
While stirring, add 285.7 parts of an aqueous solution (B-1) containing polyallylamine [trade name “PAA-15C”, concentration 15% of (B-1), manufactured by Nittobo Medical Co., Ltd.] to homogenize and solidify. Water was added so that the amount was 25.0% to obtain an aqueous dispersion (D-6).

Example 7 [Production of Aqueous Dispersion (D-7)]
In Example 1, the charged weight of (C-1) was 11.1 parts, and the aqueous solution containing polyallylamine (B-2) instead of 285.7 parts of the aqueous solution containing (B-1) [trade name "PAA". -01 ”, (B-2) concentration 15%, manufactured by Nittobo Medical Co., Ltd.] 74.1 parts were used in the same manner as in Example 1 to obtain an aqueous dispersion (D-7).

Example 8 [Production of Aqueous Dispersion (D-8)]
In Example 1, the charge weight of (C-1) was changed to 49.4 parts, and the charge weight of the aqueous solution containing (B-1) was changed from 285.7 parts to 35.1 parts. The same procedure was carried out to obtain an aqueous dispersion (D-8).

Example 9 [Production of Aqueous Dispersion (D-9)]
In Example 1, the charged weight of (C-1) was adjusted to 10.0 parts, and instead of 285.7 parts of the aqueous solution containing (B-1), polyethyleneimine (B-3) [trade name "Epomin SP-018" was used. ], Manufactured by Nippon Shokubai Co., Ltd.] An aqueous dispersion (D-9) was obtained in the same manner as in Example 1 except that 100 parts were used.

Example 10 [Production of Aqueous Dispersion (D-10)]
In Example 1, the same procedure as in Example 1 was carried out except that sodium oleate (C-2) [manufactured by Wako Pure Chemical Industries, Ltd.] was used instead of (C-1), and the aqueous dispersion (D- 10) was obtained.

Example 11 [Production of Aqueous Dispersion (D-11)]
In Example 1, an aqueous solution containing sodium alkyldiphenyl ether disulfonate (C-3) instead of (C-1) [trade name “Eleminol MON-7”, concentration 49% of (C-3), Sanyo Chemical Industries, Ltd. ( Manufactured by Co., Ltd.] The same procedure as in Example 1 was carried out except that 43.7 parts were used to obtain an aqueous dispersion (D-11).

Example 12 [Production of Aqueous Dispersion (D-12)]
In Example 1, an aqueous solution containing polyethyleneimine (B-4) instead of 285.7 parts of the aqueous solution containing (B-1) [trade name “Epomin P-1000”, concentration 30% of (B-4), Nippon Shokubai Co., Ltd.] 142.9 parts were used, but the same procedure as in Example 1 was carried out to obtain an aqueous dispersion (D-12).

Example 13 [Production of Aqueous Dispersion (D-13)]
In Example 1, 42.9 parts of tris (2-aminoethyl) amine (B-5) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 285.7 parts of the aqueous solution containing (B-1). Was carried out in the same manner as in Example 1 to obtain an aqueous dispersion (D-13).

Example 14 [Production of Aqueous Dispersion (D-14)]
In a stainless steel autoclave equipped with a stirrer and a temperature control device, 100 parts of (A-1), 23 parts of (C-1), 1.6 parts of dimethylaminoethanol and 233 parts of water were charged, and nitrogen substitution was performed twice. It was. After reducing the pressure to 0.1 MPa, the temperature was raised to 130 ° C. over 30 minutes. After stirring at 1000 rpm for 6 hours, 40 parts of the aqueous dispersion obtained by cooling to room temperature was extracted, and an aqueous solution containing polyallylamine (B-1) [trade name "PAA-15C", (B-1) Concentration 15%, manufactured by Nittobo Medical Co., Ltd.] 1413 parts, aqueous solution containing sodium dioctyl sulfosuccinate (C-4) [trade name "Sanmorin OT-70", concentration 70% of (C-4), Sanyo Kasei Kogyo ( Manufactured by Co., Ltd.] 28 parts, ethylene glycol diglycidyl ether (x-1) [manufactured by Tokyo Chemical Industry Co., Ltd.] 5.6 parts, and water 8513.4 parts are mixed so that the solid content becomes 2.5%. Aqueous dispersion (D-14) was obtained.

Example 15 [Production of Aqueous Dispersion (D-15)]
In a stainless steel autoclave equipped with a stirrer and a temperature control device, 100 parts of (A-1), 23 parts of (C-1), 1.6 parts of dimethylaminoethanol and 233 parts of water were charged, and nitrogen substitution was performed twice. It was. After reducing the pressure to 0.1 MPa, the temperature was raised to 130 ° C. over 30 minutes. After stirring at 1000 rpm for 6 hours, 202.3 parts of the aqueous dispersion obtained by cooling to room temperature was extracted, and an aqueous solution containing polyallylamine (B-1) [trade name “PAA-15C”, (B-1). ) Concentration 15%, manufactured by Nittobo Medical Co., Ltd.] 880.7 parts, (C-1) 43.6 parts, (x-1) 4.7 parts, water 8868.7 parts are mixed and the solid content is 2 An aqueous dispersion (D-15) was obtained so as to have a concentration of 5.5%.

Example 16 [Production of Composition (Y-1), Aqueous Dispersion (D-16)]
1000 parts of the aqueous dispersion (D-1) was heated at 120 ° C. in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer to evaporate the water content. After the water was removed, the mixture was stirred at 120 ° C. for 10 hours to obtain the composition (Y-1). In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 115 parts of (Y-1) was dissolved in 300 parts of THF, and 55 parts of (C-1) were added to homogenize at 60 ° C. 397 parts of water was added little by little over 15 hours to carry out phase inversion emulsification. After cooling to room temperature, tetrahydrofuran was removed under reduced pressure to obtain an aqueous dispersion (D-16).
It was confirmed by the following method that (Y-1) contained a condensate (AB).
5 g of (Y-1) was dissolved in 15 g of xylene at 130 ° C., the xylene solution was poured into 100 g of acetone, and the generated precipitate was thoroughly washed with acetone to wash away the unreacted (B-1). A sample for NMR measurement was obtained. NMR was measured on this sample, and as a peak caused by the condensate (AB), a peak caused by the structure derived from (B-1) was confirmed.

Example 17 [Production of Composition (Y-2), Aqueous Dispersion (D-17)]
In Example 16, the same procedure as in the production method of the composition (Y-1) in Example 16 was carried out except that (D-15) was used instead of (D-1), and the composition (Y-2) was prepared. Obtained. The Mn of (Y-2) was 66,000. 300 parts of (Y-2) and 700 parts of water were placed in a stainless steel autoclave equipped with a stirrer and a temperature control device, and the temperature was raised to 180 ° C. over 30 minutes. After stirring at 2000 rpm for 10 hours, the mixture was cooled to room temperature to obtain an aqueous dispersion (D-17).
It was confirmed by the following method that (Y-2) contained a condensate (AxB).
By dissolving 5 g of (Y-2) in 15 g of xylene at 130 ° C., adding the xylene solution to 100 g of acetone, and thoroughly washing the generated precipitate with acetone, unreacted (x-1) and (B). -1) was washed away to obtain a sample for NMR measurement. NMR was measured on this sample, and as peaks caused by the compound (AxB), a peak caused by the structure derived from (x-1) and a peak caused by the structure derived from (B-1) were confirmed.

Example 18 [Production of composition (Y-3)]
Concentration of aqueous solution [trade name "Carbodilite E-02", (x-2)) containing a cross-linking agent (x-2) in 1000 parts of (D-1) in a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer. 40%, manufactured by Nisshinbo Chemical Co., Ltd.] 18.5 parts were mixed and heated at 120 ° C. to evaporate the water content. After the water was removed, the mixture was stirred at 120 ° C. for 10 hours to obtain the composition (Y-3). The Mn of (Y-3) was 37,000.
It was confirmed by the following method that (Y-3) and compound (AxB) were contained.
By dissolving 5 g of (Y-3) in 15 g of xylene at 130 ° C., adding the xylene solution to 100 g of acetone, and thoroughly washing the generated precipitate with acetone, unreacted (x-2) and (B). -1) was washed away to obtain a sample for NMR measurement. NMR was measured on this sample, and as peaks caused by the compound (AxB), a peak caused by the structure derived from (x-2) and a peak caused by the structure derived from (B-1) were confirmed.

Example 19 [Production of Aqueous Dispersion (D-18)]
0.5 part of (x-1) was added to 100 parts of (D-2) to obtain an aqueous dispersion (D-18).

Example 20 [Production of Aqueous Dispersion (D-19)]
0.6 part of (x-1) was added to 100 parts of (D-3) to obtain an aqueous dispersion (D-19).

Example 21 [Production of Aqueous Dispersion (D-20)]
0.5 part of (x-1) was added to 100 parts of (D-12) to obtain an aqueous dispersion (D-20).

Example 22 [Production of Aqueous Dispersion (D-21)]
An aqueous dispersion (D-21) was obtained in the same manner as in Production Example 15 except that the charge weight of (x-1) was changed to 0.2 parts in Production Example 15.

Example 23 [Production of Aqueous Dispersion (D-22)]
An aqueous dispersion (D-22) was obtained in the same manner as in Production Example 15 except that the charge weight of (x-1) was changed to 94.4 parts in Production Example 15.

Comparative Example 1 [Production of Aqueous Dispersion (D'-1)]
In Example 1, 42.9 parts of polyether amine (B'-1) [trade name "Jeffamine M-1000", manufactured by Huntsman Co., Ltd.] was used instead of 285.7 parts of the aqueous solution containing (B-1). A comparative aqueous dispersion (D'-1) was obtained in the same manner as in Example 1 except for the above.

Comparative Example 2 [Production of Aqueous Dispersion (D'-2)]
In Example 1, the charged weight of (C-1) was changed to 30.0 parts, and N-methylethylenediamine (B'-2) [Wako Pure Chemical Industries, Ltd.] was replaced with 285.7 parts of the aqueous solution containing (B-1). Yakuhin Kogyo Co., Ltd.] The same procedure as in Example 1 was carried out except that 100 parts were used to obtain a comparative aqueous dispersion (D'-2).

<Examples 24 to 47 and Comparative Examples 3 to 4>
[Manufacture of Surface-Modified Polyolefin Nonwoven Fabrics (G-1) to (G-24) and Comparative Polyolefin Nonwoven Fabrics (G'-1) to (G'-2)]
The polyolefin non-woven fabric (PG) prepared in Production Example 12 was cut into 4 cm × 12 cm and immersed in each of the various aqueous dispersions adjusted to a predetermined solid content concentration with water according to the formulations shown in Tables 1, 2 and 5 for 10 minutes. Then, a coated product was obtained by squeezing by hand so as to be coated with a weight ratio of 100% owf (On the Weight of Fiber).
The obtained coating product was dried at 100 ° C. for 30 minutes to allow the solid content of the various aqueous dispersions to adhere to the surface, and the surface-modified polyolefin non-woven fabrics (G-1) to (G-24) and comparative polyolefins were used. Polyolefin non-woven fabrics (G'-1) to (G'-2) were obtained.

<Examples 48 to 49>
[Manufacture of Surface-Modified Polyolefin Nonwoven Fabrics (G-25) and (G-26)]
2.5 parts of the composition (Y-1) prepared in Example 16 or the composition (Y-3) prepared in Example 18 was dissolved in 97.5 parts of THF, respectively, and (Y-1) or (Y-) was dissolved. The THF solution of 3) was prepared. The polyolefin non-woven fabric (PG) prepared in Production Example 12 is cut into 4 cm × 12 cm, immersed in each of the above THF solutions for 10 minutes, and squeezed by hand so as to be coated at a weight ratio of 100% owf to obtain a coated product. It was. The obtained coating material was dried at 100 ° C. for 30 minutes to attach (Y-1) or (Y-3) to the surface, and surface-modified polyolefin non-woven fabrics (G-25) and (G-26) were obtained. Obtained.

<Example 50>
[Manufacture of surface-modified polyolefin non-woven fabric (G-27)]
In Production Example 12, instead of the commercially available polypropylene, the composition (Y-1) prepared in Example 16 and the commercially available polypropylene [trade name "SunAllomer PL500A", manufactured by SunAllomer Ltd.] are weighed 2: 8. A polyolefin non-woven fabric (G-27) was obtained in the same manner as in Production Example 12 except that a polypropylene composition melt-mixed at a ratio of 200 ° C. for 1 hour was used.

Regarding (G-1) to (G-27) and (G'-1) to (G'-2), (1) dyeability, washing fastness, color uniformity, texture, and (1) in reactive dyes 2) The dyeability, washing fastness, color uniformity, and texture of acid dyes were evaluated by the following methods. The results are shown in Tables 1-5.

<Evaluation of dyeability in reactive dyes>
Each non-woven fabric (G) is mixed with a reactive dye [trade name "Remazol Brilliant Blue R", manufactured by SIGMA-ALDRICH] at 60 ° C. in a dyeing aqueous solution of 10 g / L, anhydrous sodium sulfate 30 g / L, and sodium carbonate 10 g / L. Partial dyeing was performed, and then the non-woven fabric was washed with water. Then, in an aqueous solution of Nonipol Soft FD80 [manufactured by Sanyo Kasei Kogyo Co., Ltd.] 0.5 g / L, Sanyo Leberon [manufactured by Sanyo Kasei Kogyo Co., Ltd.] 1.0 g / L, and acetic acid 1.0 g / L at 98 ° C. After washing for a minute and then washing with water, it was allowed to stand in a constant temperature dryer [product number "OFW-300B", manufactured by AS ONE Corporation] adjusted to 50 ° C. for one day to dry.
The dried non-woven fabric was measured for L * using a spectroscopic color difference meter [product number "SD5000", manufactured by Nippon Denshoku Kogyo Co., Ltd.], and the dyeability was evaluated by the following indexes.
⊚: L * less than 30 ○: L * 30 or more and less than 50 Δ: L * 50 or more and less than 75 ×: L * 75 or more

<Evaluation of dyeability in acid dyes>
Each non-woven fabric (G) is mixed with an acid dye [trade name "Acid Blue 40", manufactured by SIGMA-ALDRICH] in a dyeing aqueous solution of 0.5 g / L, anhydrous sodium sulfate 0.5 g / L, and acetic acid 1.0 g / L. The dyeing was performed at 100 ° C. for 45 minutes, and then the non-woven fabric was washed with water. Then, in an aqueous solution of Nonipol Soft FD80 [manufactured by Sanyo Kasei Kogyo Co., Ltd.] 0.5 g / L, Sanyo Leberon [manufactured by Sanyo Kasei Kogyo Co., Ltd.] 1.0 g / L, and acetic acid 1.0 g / L at 70 ° C.15 After washing for a minute and then washing with water, it was allowed to stand in a constant temperature dryer [product number "OFW-300B", manufactured by AS ONE Corporation] adjusted to 50 ° C. for one day to dry.
The dried non-woven fabric was measured for L * using a spectroscopic color difference meter [product number "SD5000", manufactured by Nippon Denshoku Kogyo Co., Ltd.], and the dyeability was evaluated by the following indexes.
⊚: L * less than 30 ○: L * 30 or more and less than 50 Δ: L * 50 or more and less than 75 ×: L * 75 or more

<Evaluation of washing fastness>
Put each dyed non-woven fabric and 5 g / L sodium laurate aqueous solution in a container attached to a tergotometer- [model "TM-4", manufactured by Daiei Kagaku Seiki Seisakusho] under the condition of bath ratio (aqueous solution: non-woven fabric) of 50: 1. The mixture was added and stirred at 50 ° C. and 100 rpm for 30 minutes. The non-woven fabric was washed with water and allowed to stand in a constant temperature dryer [product number "OFW-300B", manufactured by AS ONE Corporation] adjusted to 50 ° C. for 1 day to dry.
L * of the dried non-woven fabric was measured using a spectroscopic color difference meter [Product No. "SD5000", manufactured by Nippon Denshoku Kogyo Co., Ltd.], and the L * before washing and the L * after washing were compared. The stainability was evaluated by the index of.
⊚: Difference between L * after washing and L * before washing is less than 10 ○: Difference between L * after washing and L * before washing is 10 or more and less than 20 Δ: L * after washing and L before washing * Difference of 20 or more and less than 30 ×: If the difference between L * after washing and L * before washing is 30 or more and the evaluation of dyeability is ×, this test is not performed.

<Evaluation of color uniformity>
The dyed non-woven fabric was visually evaluated according to the following criteria.
⊚: There is no color loss or unevenness, or it exists in a range of less than 5% of the total dyeing range.
◯: Color loss / unevenness exists in a range of 5% or more and less than 10% of the entire dyeing range.
Δ: Color loss / unevenness exists in a range of 10% or more and less than 30% of the entire dyeing range.
X: Color loss / unevenness exists in a range of 30% or more of the entire dyeing range.

<Evaluation of texture>
Each non-woven fabric after dyeing was cut to a width of 5 mm to obtain a 12 cm × 5 mm evaluation non-woven fabric without creases or bends. Place this non-woven fabric for evaluation on a flat desk, and while pressing the short side of the non-woven fabric with your finger, gradually expose the short side of the non-woven fabric from the desk. When the non-woven fabric was bent, the finger was stopped and the length of the non-woven fabric exposed from the tip of the desk was measured.
Further, instead of each non-woven fabric (G), the polyolefin non-woven fabric (PG) prepared in Production Example 12 was also evaluated in the same manner, and this was evaluated as a test result of a blank non-woven fabric according to the following criteria.
⊚: The difference obtained by subtracting the test result for the blank non-woven fabric from the evaluation result for the dyed non-woven fabric is less than +3 cm.
◯: The difference obtained by subtracting the test result for the blank non-woven fabric from the evaluation result for the dyed non-woven fabric is +3 cm or more and less than 5 cm Δ: The test result for the blank non-woven fabric was subtracted from the evaluation result for the dyed non-woven fabric. Difference is +5 cm or more and less than 8 cm ×: The difference obtained by subtracting the test result for the blank non-woven fabric from the evaluation result for the dyed non-woven fabric is +8 cm or more or does not bend.

Examples (G-1) to (G-27) of the present invention can be deeply dyed with a reactive dye and an acid dye, and have good washing fastness.
Even if the non-woven fabric is treated with an aqueous solution as in (G-1) to (G-24), or the non-woven fabric is treated with a solvent as in (G-25) to (G-26), (G) Even if it is melt-mixed with the raw material polypropylene before the production of the non-woven fabric as in −27), its dyeability does not change.
On the other hand, in (G'-1) and (G'-2) containing (B') which does not contain the above (B) and does not have a required amount of amino groups, in order to retain the reactive dye and the acid dye. Since it does not have sufficient functional groups, it cannot be dyed at all.

When a large amount of (A) and (B) is placed on the non-woven fabric, the texture of the non-woven fabric tends to be hard as shown in the result of (G-14).
Further, when the amount of (C) is small, as shown in the result of (G-3), the color uniformity tends to be deteriorated. However, the addition of a cross-linking agent as in (G-21) may improve color uniformity.
Depending on the purpose, such as when a soft dough is preferred or when an even dough is required, the treatment amount of the above (A) and the above (B) and the blending amount of the above (C) and the above (x) Need to be adjusted.

The composition of the present invention can impart excellent dyeability to a polyolefin resin. From this, the composition of the present invention, the coating agent containing the composition of the present invention, and the polyolefin molded product having the coating film of the coating agent are used for electric / electronic devices, packaging materials, transport materials, and living materials. It can be applied to a wide range of fields such as for use and for building materials. The living materials include clothing, furniture (chairs, desks, hangers, etc.), hobby supplies (sports supplies, etc.), gardening supplies (planters, etc.) and daily necessities [tableware, toys, stationery, toiletry supplies, and sanitary materials (paper diapers and masks). Etc.), etc.], etc.], etc., and the building materials include materials used for construction of houses, etc. (various doors such as entrances and interiors, interior and exterior wall materials, ceiling materials, roofing materials, heat insulating and heat insulating materials, etc.). included.

Claims (11)

At least one selected from the group consisting of an acid-modified polyolefin (A), an amine compound (B) having at least three amino groups, an anionic surfactant (C1), and a nonionic surfactant (C4). Containing with the surfactant (C) of
The anionic surfactant (C1) is a fatty acid salt and / or a sulfonic acid having an alkyl group having 8 to 24 carbon atoms.
A composition in which the nonionic surfactant (C4) is an AO (2 to 4 carbon atoms) adduct (1 to 30 moles added per active hydrogen) of a higher alcohol (8 to 32 carbon atoms). The composition according to claim 1, further comprising a cross-linking agent (x), wherein the cross-linking agent (x) satisfies at least one of the following (i) to (ii).
(I)
The cross-linking agent (x) has at least two groups selected from the group consisting of an epoxy group, an isocyanate group and a blocked isocyanate group in one molecule.
(Ii)
Crosslinker (x) has at least one carbodiimide group in one molecule. It contains a compound (AxB) and at least one surfactant (C) selected from the group consisting of an anionic surfactant (C1) and a nonionic surfactant (C4).
The anionic surfactant (C1) is a fatty acid salt and / or a sulfonic acid having an alkyl group having 8 to 24 carbon atoms.
A composition in which the nonionic surfactant (C4) is an AO (2 to 4 carbon atoms) adduct (1 to 30 moles added per active hydrogen) of a higher alcohol (8 to 32 carbon atoms). There,
The compound (AxB) is a compound obtained by cross-linking an acid-modified polyolefin (A) and an amine compound (B) having at least three amino groups with a cross-linking agent (x).
A composition in which the cross-linking agent (x) satisfies at least one of the following (i) to (ii).
(I)
The cross-linking agent (x) has at least two groups selected from the group consisting of an epoxy group, an isocyanate group and a blocked isocyanate group in one molecule.
(Ii)
Crosslinker (x) has at least one carbodiimide group in one molecule. The composition according to any one of claims 1 to 3 , wherein the acid value of the acid-modified polyolefin (A) is 1 to 12 mgKOH / g. The composition according to any one of claims 1 to 4 , wherein the primary amine value of the amine compound (B) is 250 to 1,200 mgKOH / g. A coating agent containing the composition according to any one of claims 1 to 5. A polyolefin molded product containing the composition according to any one of claims 1 to 5. A polyolefin molded product having a coating film of the coating agent according to claim 6 on the surface of a polyolefin base material. A polyolefin molded product having a coating film containing the composition according to any one of claims 1 to 5 on the surface of a polyolefin base material. The polyolefin molded product according to claim 8 or 9 , wherein the weight of the coating film is 0.1 to 10% by weight based on the weight of the polyolefin molded product. The polyolefin molded product according to any one of claims 7 to 10 , further containing a dye (F).