CN114787272A - Aqueous resin composition, aqueous surface treatment agent, and article - Google Patents

Abstract

The subject to be solved by the present invention is to provide an aqueous resin composition excellent in abrasion resistance and touch. The present invention provides an aqueous resin composition comprising an aqueous polyurethane (A) using piperazine and/or hydrazine as essential raw materials, an acid-modified non-chlorinated polyolefin (B), a matting agent (C) and a crosslinking agent (D). In addition, the present invention provides an aqueous surface treatment agent characterized by containing the above-mentioned aqueous resin composition; and an article characterized by having a coating film of the aqueous resin composition. The water-based resin composition of the invention can make the surface of various articles matte tones, impart a more advanced design, and also has high adhesion to difficult-to-adhesion substrates such as polyolefins, even when stretched, etc. Even in the molding process, a coating film having an excellent matte feel can be obtained by one coating.

Description

Water-based resin composition, water-based surface treatment agent and articles

technical field

The present invention relates to aqueous resin compositions, aqueous surface treatment agents and articles.

Background technique

In the manufacturing process of the thermoplastic olefin (Thermo Plastic Olefin; hereinafter abbreviated as "TPO") leather sheet for automobile interiors, it is finished with a surface treatment agent from the viewpoint of imparting durability and designability to the surface. The mainstream of the resin composition used in the conventional surface treatment agent is a solvent system containing an organic solvent, but with the improvement of environmental restrictions in recent years, the development of an aqueous surface treatment agent that does not substantially contain an organic solvent is advancing (for example, Refer to Patent Document 1).

However, there is room for improvement in abrasion resistance and touch, and improvement of these properties is strongly demanded.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2010-121027

SUMMARY OF THE INVENTION

The problem to be solved by the invention

The subject to be solved by the present invention is to provide an aqueous resin composition excellent in abrasion resistance and touch.

means of solving problems

The present invention provides an aqueous resin composition comprising an aqueous polyurethane (A) using piperazine and/or hydrazine as essential raw materials, an acid-modified non-chlorinated polyolefin (B), a matting agent (C) and a crosslinking agent (D).

In addition, the present invention provides an aqueous surface treatment agent characterized by containing the above-mentioned aqueous resin composition; and an article characterized by having a coating film of the aqueous surface treatment agent.

Invention effect

The aqueous resin composition of the present invention is excellent in abrasion resistance and touch. In addition, the surface of various items can be made into a matte tone to give a more advanced design, and it has high adhesion to difficult-to-adhesion substrates such as polyolefin, even if it is subjected to forming processes such as stretching. Since a coating film with an excellent matte feel can be obtained by one coating, it can be used as a treatment agent on the surface of various articles. In particular, it can be suitably used for plastic molded products, and among plastic molded products, it can be more suitably used for TPO leather and TPO sheet which are molded products of thermoplastic olefin (Thermo Plastic Olefin; hereinafter abbreviated as "TPO").

Detailed ways

The aqueous resin composition of the present invention contains an aqueous polyurethane (A) using piperazine and/or hydrazine as essential raw materials, an acid-modified non-chlorinated polyolefin (B), a matting agent (C) and a crosslinking agent (D).

The above-mentioned water-based polyurethane (A) must use piperazine and/or hydrazine as a raw material in order to obtain excellent abrasion resistance and touch. The piperazine and hydrazine are called chain extenders in the raw materials of water-based polyurethane, and generate urea bonds. This urea bond constitutes a hard segment in the polyurethane resin. Both the piperazine and the hydrazine have very short chain lengths, so that very cohesive hard segments can be built. For the above reasons, it is possible to impart excellent abrasion resistance and a touch without stickiness.

The above-mentioned "water-based" in the above-mentioned water-based polyurethane resin (A) means that the above-mentioned water-based polyurethane resin (A) can be dispersed in water, and for example, hydrophilic groups having an anionic group, a cationic group, and a nonionic group can be used. Agglomerated polyurethane resins; polyurethane resins that are forcibly dispersed in water with an emulsifier, etc. These aqueous polyurethane resins (A) may be used alone or in combination of two or more.

As a method of obtaining the urethane resin which has the said anionic group, the method of using, as a raw material, one or more compounds selected from the group which consists of a compound which has a carboxyl group and a compound which has a sulfonyl group is mentioned, for example.

As a compound which has the said carboxyl group, 2, 2- dimethylol propionic acid, 2, 2- dimethylol butyric acid, 2, 2- dimethylol butyric acid, 2, 2- dimethylol can be used, for example propionic acid, 2,2-valeric acid, etc. These compounds may be used alone or in combination of two or more.

As the compound having the above-mentioned sulfonyl group, for example, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2- aminoethyl)-2-aminoethylsulfonic acid, etc. These compounds may be used alone or in combination of two or more.

The above-mentioned carboxyl group and sulfonyl group may be partially or completely neutralized by a basic compound in the resin composition. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal alkali compounds containing sodium, potassium, lithium, calcium, and the like.

As a method of obtaining the urethane resin which has the said cationic group, the method of using 1 type or 2 or more types of the compound which has an amino group as a raw material is mentioned, for example.

As the above-mentioned compound having an amino group, for example, compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyl groups such as N-methyldiethanolamine and N-ethyldiethanolamine can be used Compounds having tertiary amino groups, such as N-alkyldiaminoalkylamines such as dialkanolamines, N-methyldiaminoethylamines, and N-ethyldiaminoethylamines, and the like. These compounds may be used alone or in combination of two or more.

As a method of obtaining the urethane resin which has the said nonionic group, the method of using 1 type or 2 or more types of the compound which has an oxyethylene structure as a raw material is mentioned, for example.

As a compound which has the said oxyethylene structure, the polyether polyol which has an oxyethylene structure, such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, can be used, for example. These compounds may be used alone or in combination of two or more.

From the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, weather resistance, touch, and hydrolysis resistance, the amount of the raw material used for the production of the above-mentioned hydrophilic group-containing polyurethane resin is higher in water-based The range of 0.1-15 mass % is preferable in the raw material of a polyurethane resin (A), the range of 1-10 mass % is more preferable, and the range of 1.5-7 mass % is more preferable.

As an emulsifier that can be used to obtain the above-mentioned urethane resin that is forcibly dispersed in water, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, Nonionic emulsifiers such as polyoxyethylene sorbitan tetraoleate and polyoxyethylene-polyoxypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkyl benzene sulfonates, alkyl Anionic emulsifiers such as sulfosuccinate, naphthalene sulfonate, polyoxyethylene alkyl sulfate, alkanesulfonic acid sodium salt, alkyl diphenyl ether sulfonic acid sodium salt; alkyl amine salt, alkyl trimethylene Cationic emulsifiers such as ammonium salts, alkyl dimethyl benzyl ammonium salts, etc. These emulsifiers may be used alone or in combination of two or more.

As the water-based polyurethane resin (A), specifically, for example, raw materials for producing the above-mentioned hydrophilic group-containing polyurethane resin, polyisocyanate (a1), polyol (a2), and hydrazine and/or containing Reactant for chain extender (a3) of piperazine. For their reaction, a known urethanization reaction can be used.

As said polyisocyanate (a1), for example, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate can be used. , Aromatic polyisocyanates such as carbodiimide diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate , aliphatic or alicyclic polyisocyanates such as xylylene diisocyanate, tetramethyl xylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc. These polyisocyanates may be used alone or in combination of two or more.

As the polyisocyanate (a1), from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, alicyclic polyisocyanates are preferably used, and nitrogen having at least one isocyanate group is more preferably used. Polyisocyanates having a structure in which atoms and a cyclohexane ring are directly connected, isophorone diisocyanate and/or dicyclohexylmethane diisocyanate are more preferably used, and from the viewpoint of further improving the workability during stretching, more preferred. Isophoronediamine is preferred. In addition, the amount of the alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1), more preferably 30% by mass or more, from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. 40 mass % or more, More preferably, it is 50 mass % or more.

In addition, when using the aqueous resin composition of the present invention as a surface treatment agent, when further light resistance and processability during stretching are required, it is preferable to use the above-mentioned alicyclic polyisocyanate together as the above-mentioned polyisocyanate (a1). Isocyanates and aliphatic polyisocyanates, as the above-mentioned aliphatic polyisocyanates, hexamethylene diisocyanate is preferably used. As content of the said alicyclic polyisocyanate in polyisocyanate (a1) at this time, 30 mass % or more is preferable, 40 mass % or more is more preferable, and 50 mass % or more is still more preferable.

The amount of the polyisocyanate (a1) used is preferably in the range of 5 to 50% by mass in the raw material of the polyurethane resin (A) from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. , the range of 15-40 mass % is more preferable, and the range of 20-37 mass % is further more preferable.

As said polyol (a2), a polyether polyol, a polyester polyol, a polyacrylic acid polyol, a polycarbonate polyol, a polybutadiene polyol, etc. can be used, for example. These polyols may be used alone or in combination of two or more. Among them, polycarbonate polyols are preferably used from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance.

As the above-mentioned polycarbonate polyol, for example, a reaction product of carbonate and/or phosgene and a compound having two or more hydroxyl groups can be used.

As said carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. can be used, for example. These compounds may be used alone or in combination of two or more.

As the compound having two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2 -Methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol Alcohol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,10-Decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, 3-methylpentanediol Alcohol, neopentyl glycol, trimethylolethane, glycerin, etc. These compounds may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance, those selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,5-pentanediol are preferably used. 1 or more compounds selected from the group consisting of ,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and 1,10-decanediol, more preferably 1,6-hexanediol .

The usage-amount of the above-mentioned polycarbonate polyol is preferably 85% by mass or more, more preferably 90% by mass in the polyol (a2), from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, and weather resistance. The mass % or more is more preferably 95 mass % or more.

The number average molecular weight of the above-mentioned polycarbonate polyol is preferably in the range of 100 to 100,000, and more preferably 150 to 10,000, from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, abrasion resistance, and weather resistance. The range of 200-2,500 is more preferable. In addition, the number average molecular weight of the said polycarbonate polyol shows the value measured by the gel permeation column chromatography (GPC) method.

From the viewpoint of obtaining more excellent weather resistance, the number average molecular weight of the above-mentioned polyol (a2) other than the above-mentioned polycarbonate polyol is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 50,000, and still more preferably in the range of 800 to 10,000. In addition, the number average molecular weight of the said polyol (a2) shows the value measured by the gel permeation column chromatography (GPC) method.

As the usage-amount of the said polyol (a2), in the raw material of the polyurethane resin (A), it is preferable that it is the range of 30-80 mass %, the range of 40-75 mass % is more preferable, the range of 50-70 mass % is more preferable scope.

As the chain extender (a3), as described above, hydrazine and/or piperazine must be used, and the amount of the chain extender (a3) used is more preferably 50% by mass or more, further preferably 60% by mass or more, It is especially preferable that it is 80 mass % or more. In addition, as the chain extender (a3), the average number of functional groups is preferably less than 3, more preferably less than 2.5.

As the chain extender (a3) that can be used other than the above-mentioned hydrazine and/or piperazine, for example, a chain extender having a number average molecular weight in the range of 50 to 450 (excluding the above-mentioned polycarbonate polyol) can be used. Specifically, Use ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine , 1,4-cyclohexanediamine and other chain extenders with amino groups; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-Butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerol, sorbitol, bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy A chain extender having a hydroxyl group such as diphenyl ether and trimethylolpropane, and the like. These chain extenders may be used alone or in combination of two or more.

The usage-amount of the chain extender (a3) is preferably 0.5 in the raw material of the polyurethane resin (A) from the viewpoint of obtaining more excellent chemical resistance, mechanical strength, abrasion resistance, touch, and weather resistance. The range of -10 mass % is more preferable in the range of 0.7-5 mass %, and the range of 0.9-2.3 is still more preferable.

As a method for producing the above-mentioned aqueous polyurethane resin (A), for example, by reacting the above-mentioned polyisocyanate (a1), the above-mentioned polyol (a2) and the raw material for producing the above-mentioned hydrophilic group-containing polyurethane resin, Thus, a method of producing a urethane prepolymer having an isocyanate group, followed by reacting the above-mentioned urethane prepolymer with the above-mentioned chain extender (a3); the above-mentioned polyisocyanate (a1), the above-mentioned polyvalent The alcohol (a2), the raw material for producing the urethane resin having a hydrophilic group, and the above-mentioned chain extender (a3) are charged at once and reacted, and the like. These reactions can be carried out, for example, at 50 to 100°C for 3 to 10 hours.

The total of the hydroxyl group which the raw material for producing the polyurethane resin having a hydrophilic group has, the hydroxyl group which the polyol (a2) has, and the hydroxyl group and amino group which the chain extender (a3) has is the same as the polyol (a3). The molar ratio of the isocyanate group in the isocyanate (a1) [(isocyanate group)/(hydroxyl group and amino group)] is preferably in the range of 0.8 to 1.2, and more preferably in the range of 0.9 to 1.1.

When producing the above-mentioned aqueous polyurethane resin (A), it is preferable to deactivate the isocyanate group remaining in the above-mentioned polyurethane resin (A). When deactivating the said isocyanate group, it is preferable to use the alcohol which has one hydroxyl group, such as methanol. As a usage-amount of the said alcohol, it is preferable that it is the range of 0.001-10 mass parts with respect to 100 mass parts of urethane resins (A).

Moreover, when manufacturing the said aqueous polyurethane resin (A), an organic solvent can be used. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; Amide compounds such as methylpyrrolidone, etc. These organic solvents may be used alone or in combination of two or more. In addition, it is preferable that the said organic solvent is finally removed by distillation etc..

The content of the urethane bond in the aqueous polyurethane resin (A) is preferably in the range of 980 to 4,000 mmol/kg from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, touch, and weather resistance , more preferably in the range of 1,000 to 3,500 mmol/kg, still more preferably in the range of 1,100 to 3,000 mmol/kg, still more preferably in the range of 1,150 to 2,500 mmol/kg. In addition, the content of the urethane bond of the said urethane resin (A) is represented by the said polyisocyanate (a1), the polyol (a2), the raw material for producing the urethane resin which has a hydrophilic group, and The value calculated from the input amount of the chain extender (a3).

The content of the urea bond in the aqueous polyurethane resin (A) is preferably in the range of 315 to 850 mmol/kg from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, touch and weather resistance, and more preferably The range of 350-830 mmol/kg, the range of 400-800 mmol/kg is more preferable, the range of 410-770 mmol/kg is further more preferable. In addition, the content of the urea bond of the said urethane resin (A) is represented by the said polyisocyanate (a1), the polyol (a2), the raw material for producing the urethane resin which has a hydrophilic group, and the chain extender The value calculated from the input amount of (a3).

The content of the alicyclic structure of the urethane resin (A) is preferably in the range of 500 to 3,000 mmol/kg, more preferably from the viewpoint of obtaining more excellent chemical resistance, abrasion resistance, touch, and weather resistance. It is the range of 600-2,900 mmol/kg, More preferably, it is the range of 700-2,700 mmol/kg. In addition, the content of the alicyclic structure of the said urethane resin (A) is represented by the said polyisocyanate (a1), the polyol (a2), the raw material for producing the urethane resin which has a hydrophilic group, and the chain extension The value calculated from the input amount of the agent (a3).

The content of the above-mentioned aqueous polyurethane resin (A) is preferably in the range of 1 to 30 mass % in the polyurethane resin composition, and more preferably 2 to 20 mass %, from the viewpoints of coatability, workability, and storage stability. % range.

The content (solid content) of the above-mentioned aqueous polyurethane resin (A) is preferably in the range of 1 to 30 mass % in the aqueous resin composition from the viewpoints of coatability, workability, and storage stability, and more preferably The range of 3-28 mass %.

The acid-modified non-chlorinated polyolefin (B) is a polyolefin acid-modified without chlorinating the polyolefin. The above-mentioned polyolefin is obtained by polymerizing an olefin compound, and as the above-mentioned olefin compound, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, and 1-hexene can be used. - Nonene, etc. In addition, these olefin compounds may be used alone or in combination of two or more, and the polyolefin (B) may be a homopolymer or a copolymer.

Examples of the polyolefin used as a raw material for the polyolefin (B) include polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, natural rubber, synthetic isopropylene rubber, and ethylene-vinyl acetate copolymer. Wait. Moreover, when the said polyolefin (B) is a copolymer, a random copolymer may be sufficient, and a block copolymer may be sufficient as it.

The polyolefin (B) described above is obtained by acid-modifying the polyolefin exemplified above, and the acid-modification is preferably a method of reacting with the polyolefin using an unsaturated carboxylic acid or an acid anhydride thereof. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, crotonic acid, and the like. of acid anhydrides. Moreover, half ester, half amide, etc. of an unsaturated carboxylic acid are mentioned. Among these unsaturated carboxylic acids, acrylic acid, methacrylic acid, maleic acid or maleic anhydride is preferably used.

The acid modification of the polyolefin can be carried out, for example, by mixing a polyolefin dissolved in an organic solvent with an unsaturated carboxylic acid, and heating and reacting it at a temperature equal to or higher than the softening temperature or the melting point of the polyolefin.

The content ratio (solid content) of the polyolefin (B) is preferably in the range of 0.5 to 30 mass % in the aqueous resin composition, and more preferably 0.6 from the viewpoints of coatability, workability, and storage stability. The range of -25 mass %.

The mass ratio [(A)/(B)] of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B) is preferably 55 from the viewpoint of obtaining high adhesion to a substrate such as TPO. /45 to 98/2, more preferably 60/40 to 98/2, still more preferably 70/30 to 97/3.

Examples of the above-mentioned matting agent (C) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, Aluminosilicates, etc.

As said silica particle, dry silica, wet silica, etc. are mentioned. Among them, dry silica is preferable because the scattering effect is high and the adjustment range of the gloss value is widened. In addition, dry silica surface-modified with an organic compound is more preferable from the viewpoint of being easily dispersed in the composition. The average particle diameter of these silica particles is preferably in the range of 2 to 14 μm, and more preferably in the range of 3 to 12 μm.

The amount of the silica particles to be used is based on the amount of the above-mentioned water-based polyurethane (A) and acid-modified non-chlorinated polyolefin (B) from the viewpoint of achieving a gloss value at which a desired matte tone design can be obtained. The total resin component is 100 parts by mass, preferably in the range of 0.1 to 40 parts by mass, and more preferably in the range of 0.5 to 30 parts by mass.

As said organic beads, acrylic beads, urethane beads, silicon beads, olefin beads, etc. are mentioned, for example.

The above-mentioned matting agent (C) may be used alone or in combination of two or more.

Examples of the crosslinking agent (D) include urea resin-based crosslinking agents such as oxazoline, carbodiimide, polyisocyanate, blocked isocyanate, epoxy resin, polysiloxane, aziridine, and alkylated melamine. Linking agent, hydrazide-based cross-linking agent, etc. Among them, carbodiimide and polyisocyanate are preferred from the viewpoint of crosslinking performance and safety. Moreover, these crosslinking agents (D) may be used 1 type, and may use 2 or more types together. The compounding amount of the crosslinking agent (D) is preferably 100 parts by mass of the total resin component of the aqueous polyurethane (A) and the acid-modified non-chlorinated polyolefin (B) from the viewpoint of the strength of the coating film. The range of 0.5-50 mass parts is more preferably the range of 1-40 mass parts.

The aqueous resin composition of the present invention contains the above-mentioned aqueous polyurethane (A), the above-mentioned acid-modified non-chlorinated polyolefin (B), the above-mentioned matting agent (C) and the above-mentioned crosslinking agent (D) as essential components, and may be used as necessary. Contains other additives.

As the above-mentioned other additives, various surfactants, waxes, antifoaming agents, leveling agents, viscoelasticity modifiers, wetting agents, dispersing agents, preservatives, film-forming agents, plasticizers, penetrants, fragrances can be blended, for example. , fungicides, acaricides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (such as titanium white, iron oxide red, phthalocyanine, carbon black, permanent yellow, etc.), Additives such as water and solvents.

The article of the present invention has a coating film of the aqueous resin composition of the present invention. In addition, examples of articles include housings of home appliances (refrigerators, washing machines, air conditioners, televisions, etc.), housings of electronic devices (personal computers, mobile phones, smartphones, etc.), musical instruments (pianos, electric pianos, etc.) , electronic musical instruments, etc.); interior materials of automobiles or railway vehicles (instrument panels, door trims, headliners, rear seat panels, etc.), building materials or furniture materials (wallpaper, decorative sheets for plywood, steel plates, etc.) Plastic moldings such as decorative sheets, leather for chair sticking, etc.), packaging materials (polishing films, etc.); wood materials (plywood, integrated materials, single-layer laminate materials, etc.); ceramic materials (internal tiles, bricks, etc.). Sports (skiing, archery, golf, tennis, etc.) equipment materials; shoe materials (shoe back, sole, core material, heel, heel surface, insole, etc.); metal materials (iron, copper, zinc, aluminum, etc.) etc. Among these articles, the aqueous resin composition of the present invention can be suitably used for plastic molded articles, and among the plastic molded articles, TPO leather and TPO sheets are preferably used.

Example

Hereinafter, the present invention will be specifically described by way of examples.

[Synthesis example 1] Preparation of aqueous polyurethane resin (A-1) composition

250 parts by mass of methyl ethyl ketone and 0.001 part by mass of stannous octoate were added to a four-necked flask equipped with a stirrer, a thermometer and a nitrogen reflux tube, followed by polycarbonate polyol-1 (with 1,4-butanediol and 1,6-hexanediol). Diol as raw material, number average molecular weight: 1,000) 200 parts by mass, 15 parts by mass of 2,2-dimethylolpropionic acid, 49 parts by mass of isophorone diisocyanate, 34 parts by mass of hexamethylene diisocyanate, in The reaction was carried out at 70°C for 1 hour to obtain a methyl ethyl ketone solution of the urethane prepolymer.

Next, after mixing 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine in the methyl ethyl ketone solution of the urethane prepolymer, 820 parts by mass of ion-exchanged water was added to obtain a urethane resin (A-1) dispersed in Emulsion in water.

Next, methyl ethyl ketone was distilled off from the said emulsification liquid, and ion-exchange water was further added, and the water-based polyurethane resin (A-1) composition of 30 mass % of nonvolatile content was obtained.

The obtained aqueous polyurethane resin (A-1) had a urethane bond content of 2,052 mmol/kg, a urea bond content of 698 mmol/kg, and an alicyclic structure content of 715 mmol/kg.

[Synthesis example 2] Preparation of aqueous polyurethane resin (A-2) composition

250 parts by mass of methyl ethyl ketone and 0.001 part by mass of stannous octoate were added to a four-necked flask equipped with a stirrer, a thermometer and a nitrogen reflux tube, and then, polycarbonate polyol-3 (using 1,6-hexanediol as a raw material, several Average molecular weight: 2,000) 220 parts by mass, 12 parts by mass of 2,2-dimethylolpropionic acid, 70 parts by mass of dicyclohexylmethane diisocyanate, and reacted at 70° C. for 1 hour to obtain methyl ethyl ketone of a urethane prepolymer solution.

Next, after mixing 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine in the methyl ethyl ketone solution of the urethane prepolymer, 880 parts by mass of ion-exchanged water was added to obtain a urethane resin (A-2) dispersion. Emulsion in water.

Next, methyl ethyl ketone was distilled off from the said emulsification liquid, and ion-exchange water was further added, and the water-based polyurethane resin (A-2) composition of 32 mass % of nonvolatile content was obtained.

The obtained aqueous polyurethane resin (A-2) had a urethane bond content of 1,278 mmol/kg, a urea bond content of 435 mmol/kg, and an alicyclic structure content of 1,713 mmol/kg.

[Comparative Synthesis Example 1] Preparation of Aqueous Polyurethane Resin (AR-1) Composition

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas injection pipe, 500 parts by mass of polycarbonate diol (using 1,6-hexanediol as a raw material, number average molecular weight: 1,000) was charged under nitrogen flow. , 34 parts by mass of 2,2-dimethylolpropionic acid, and 336 parts by mass of methyl ethyl ketone, and mixed uniformly. Then, after adding 250 parts by mass of isophorone diisocyanate, 0.1 part by mass of dibutyltin dilaurate was added, and the reaction was carried out at 70° C. for about 4 hours to obtain a urethane prepolymer (resin) having an isocyanate group at the molecular end. NCO% in solid content: 4.0 mass %) methyl ethyl ketone solution.

Next, 25 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained above to neutralize the carboxyl groups in the urethane prepolymer. Then, after adding 1,471 parts by mass of ion-exchanged water, 23 parts by mass of ethylenediamine was added and reacted. After completion of the reaction, methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurethane resin (AR-1) composition (solid content: 35% by mass).

[Example 1]

40.5 parts by mass of the aqueous polyurethane resin (A-1) composition obtained in Production Example 1, 15.9 parts by mass of acid-modified non-chlorinated polyolefin (“ARROWBASE SD-1010” manufactured by Unitika Co., Ltd., nonvolatile matter: 20.5 parts by mass %), 5.2 parts by mass of cross-linking agent (“CARBODILITE E-04” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide-based cross-linking agent, nonvolatile content: 40 mass %), 2.2 parts by mass of matting agent (Evonik Degussa "ACEMATT 3300" manufactured by the company, silica particles whose surface was organically treated by a dry method, average particle size: 9.5 μm), 1 part by mass of polypropylene wax (“MICROMATTE 1213UVW” manufactured by MicroPowders Corporation; melting range 150 to 156° C.), 0.1 part by mass of nonionic surfactant (“Noigen EA-157” manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), 0.1 part by mass of fluorine-based surfactant (“Megafac F-444” manufactured by DIC Corporation) ), 0.7 parts by mass of a viscoelasticity modifier ("SN Thickener 612NC" manufactured by SANNOPCO Co., Ltd.), and 36.9 parts by mass of ion-exchanged water were uniformly mixed to obtain an aqueous resin composition (1).

[Example 2]

In Example 1, except having used the aqueous polyurethane resin (A-2) composition instead of the aqueous polyurethane resin (A-1) composition, it carried out similarly to Example 1, and obtained the aqueous resin composition (2).

[Example 3]

48 parts by mass of the aqueous polyurethane resin (A-1) composition obtained in Production Example 1, 4 parts by mass of acid-modified non-chlorinated polyolefin (“ARROWBASE SD-1010” manufactured by Unitika Co., Ltd., nonvolatile content: 20.5 mass parts) %), 5.2 parts by mass of cross-linking agent (“CARBODILITE E-04” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide-based cross-linking agent, nonvolatile content: 40 mass %), 2.2 parts by mass of matting agent (Evonik Degussa "ACEMATT 3300" manufactured by the company, silica particles whose surface was organically treated by a dry method, average particle size: 9.5 μm), 1 part by mass of polypropylene wax (“MICROMATT 1213UVW” manufactured by MicroPowders Corporation; melting range 150 to 156° C.), 0.1 part by mass of nonionic surfactant (“Noigen EA-157” manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), 0.1 part by mass of fluorine-based surfactant (“Megafac F-444” manufactured by DIC Corporation) ), 0.7 parts by mass of a viscoelasticity modifier ("SN Thickener 612NC" manufactured by SANNOPCO Co., Ltd.), and 41.3 parts by mass of ion-exchanged water were uniformly mixed to obtain an aqueous resin composition (3).

[Example 4]

In Example 3, except having used the aqueous polyurethane resin (A-2) composition instead of the aqueous polyurethane resin (A-1) composition, it carried out similarly to Example 1, and obtained the aqueous resin composition (4).

[Comparative Example 1]

In Example 1, except having used the aqueous polyurethane resin (AR-1) composition instead of the aqueous polyurethane resin (A-1) composition, it carried out similarly to Example 1, and obtained the aqueous resin composition (R).

[Preparation of samples for evaluation]

The aqueous resin compositions obtained in Examples and Comparative Examples were coated on TPO leather (thickness 0.4 mm) using bar coater No. 14, and then dried at 120° C. for 1 minute to obtain samples for evaluation.

[Evaluation method of abrasion resistance]

The samples for evaluation were evaluated as follows by observing the wear state using a Gakushin-type friction tester (“RT-200” manufactured by Daiei Scientific Seiki Co., Ltd.) and using No. 6 canvas under a load of 1 kg.

"T": TPO leather was not exposed after 100 tests.

"F": The coating film was broken after 100 tests, and the TPO leather was exposed.

[Evaluation method of touch]

The sample for evaluation was touched by finger, and the evaluation was performed as follows.

"T": No stickiness.

"F": There is stickiness.

[Table 1]

It turned out that Examples 1-4 which are the aqueous resin compositions of this invention have excellent abrasion resistance and a touch.

On the other hand, in Comparative Example 1, the water-based polyurethane resin using ethylenediamine as a raw material was used instead of the water-based polyurethane resin (A), but the abrasion resistance and the touch were poor.

Claims (3)

1. An aqueous resin composition comprising an aqueous polyurethane (A) containing piperazine and/or hydrazine as essential raw materials, an acid-modified non-chlorinated polyolefin (B), a matting agent (C), and a crosslinking agent (D).

2. An aqueous surface treatment agent characterized by comprising the aqueous resin composition according to claim 1.

3. An article comprising a coating film of the aqueous resin composition according to claim 1.