JP7334802B2 - Surface treatment layer and article - Google Patents

Description

TECHNICAL FIELD The present invention relates to surface treatment layers and articles.

In the manufacturing process of thermoplastic olefin resin (TPO) leather seats for automotive interiors, the surface is finished with a surface treatment agent from the viewpoint of imparting durability and design. Solvent-based resin compositions containing organic solvents have been the mainstream materials used for conventional surface treatment agents, but in response to recent heightened environmental regulations, water-based surface treatment agents that do not substantially contain organic solvents are becoming popular. Development is underway.

Furthermore, along with the diversification of the design of automobiles, there is a growing demand for finish that emphasizes the design of instrument panels and door trims. However, with the current water-based surface treatment agent (see, for example, Patent Document 1), when molded into a shape designed by a designer of an automobile manufacturer, a portion where the molded product is highly stretched locally occurs at the end. , only that portion has a high gloss, and the design property is impaired. In addition to this, there is a strong demand from the market to improve the peel strength against TPO leather and the ethanol resistance of the surface treatment layer.

JP 2006-176615 A

The problem to be solved by the present invention is to provide a surface treatment layer that uses a water-containing material, has little change in gloss during stretching, and has excellent peel strength and ethanol resistance.

The present invention provides a surface treatment layer having a primer layer (i) and a topcoat layer (ii), wherein the primer layer (i) comprises a urethane resin (A), an olefin resin (B), a filler (C ), and a primer layer-forming resin composition containing water (D), the gloss value of the primer layer (i) is less than 0.9, and the topcoat layer (ii ) is formed from a topcoat layer-forming resin composition containing urethane resin (X), beads (Y), and water (Z), and the beads ( The present invention provides a surface treatment layer characterized in that the filling rate of Y) is in the range of 25 to 90%.

The present invention also provides an article comprising a thermoplastic olefin resin substrate and the surface treatment layer.

Since the surface treatment layer of the present invention uses a material containing water, it is environmentally friendly, exhibits little change in gloss during stretching, and is excellent in peel strength and ethanol resistance. In particular, the surface treatment layer of the present invention has excellent peel strength against TPO leather.

The surface treatment layer of the present invention has a primer layer (i) and a topcoat layer (ii), and it is essential that each layer is made of a specific material.

The primer layer (i) may contain a urethane resin (A) and an olefin resin (B) in order to obtain particularly excellent adhesion (peel strength) to TPO leather and ethanol resistance. In addition, it contains a filler (C), which is a matting agent, in order to suppress a change in glossiness during stretching of the surface treatment layer, and the filler (C) reduces the glossiness of the primer layer (i) to 0. Must be less than 9.

The urethane resin (A) is dispersible in water (D), for example, a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; B) A urethane resin or the like dispersed therein can be used. These urethane resins (A) may be used alone or in combination of two or more.

Examples of the method for obtaining the urethane resin having an anionic group include a method using, as a raw material, one or more compounds selected from the group consisting of compounds having a carboxyl group and compounds having a sulfonyl group.

Examples of compounds having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpropionic acid, and 2,2-dimethylolpropionic acid. Herbal acid or the like can be used. These compounds may be used alone or in combination of two or more.

Examples of compounds having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)- 2-Aminoethylsulfonic acid and the like can be used. These compounds may be used alone or in combination of two or more.

The carboxyl groups and sulfonyl groups may be partially or wholly neutralized with 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 base compounds containing sodium, potassium, lithium, calcium, and the like. can be done.

Examples of the method for obtaining the urethane resin having a cationic group include a method using one or more compounds having an amino group as raw materials.

Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamine such as N-methyldiethanolamine and N-ethyldiethanolamine; Compounds having a tertiary amino group such as N-alkyldiaminoalkylamines such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.

Examples of the method for obtaining the urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as raw materials.

Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.

The amount of the raw material used to produce the urethane resin having the above hydrophilic groups is such that it has better adhesion to TPO leather, suppression of gloss change during stretching, chemical resistance, abrasion resistance, and weather resistance. , and, from the viewpoint of obtaining hydrolysis resistance, it is preferably in the range of 0.1 to 15% by mass in the raw material of the urethane resin (A), more preferably in the range of 1 to 10% by mass, and 1.5 A range of ~7% by mass is more preferred.

Examples of emulsifiers that can be used to obtain the urethane resin that is forcibly dispersed in water (D) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene nonionic emulsifiers such as ethylene sorbitol tetraoleate and polyoxyethylene/polyoxypropylene copolymer; Anionic emulsifiers such as polyoxyethylene alkyl sulfates, alkanesulfonate sodium salts, and alkyldiphenyl ether sulfonate sodium salts; and cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. can. These emulsifiers may be used alone or in combination of two or more.

Specific examples of the urethane resin (A) include, for example, raw materials used for producing the urethane resin having a hydrophilic group, a polyisocyanate (a1), a polyol (a2), and a chain extender ( The reactants of a3) can be used. A known urethanization reaction can be used for these reactions.

Examples of the polyisocyanate (a1) include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate; , lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

As the polyisocyanate (a1), an alicyclic polyisocyanate is selected from the viewpoint of achieving even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, abrasion resistance, and weather resistance. is preferably used, more preferably a polyisocyanate having one or more structures in which at least the nitrogen atoms of the isocyanate group are directly linked to a cyclohexane ring, and isophorone diisocyanate and/or dicyclohexylmethane diisocyanate are more preferably used. Further, the amount of the alicyclic polyisocyanate used is preferably 30% by mass or more in the polyisocyanate (a1) from the viewpoint of obtaining even better chemical resistance, abrasion resistance, and weather resistance. , more preferably 40% by mass or more, and even more preferably 50% by mass or more.

Further, when further light resistance is required for the surface treatment layer of the present invention, it is preferable to use the alicyclic polyisocyanate and the aliphatic polyisocyanate in combination as the polyisocyanate (a1). Hexamethylene diisocyanate is preferably used as the aliphatic polyisocyanate. At this time, the content of the alicyclic polyisocyanate in the polyisocyanate (a1) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more.

The amount of the polyisocyanate (a1) to be used is urethane resin from the viewpoint of obtaining even better adhesion to TPO leather, suppression of gloss change during stretching, chemical resistance, abrasion resistance, and weather resistance. It is preferably in the range of 5 to 50% by mass, more preferably in the range of 15 to 40% by mass, and even more preferably in the range of 20 to 37% by mass in the raw material of (A).

As the polyol (a2), for example, polyether polyol, polyester polyol, polyacrylic polyol, polycarbonate polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polycarbonate polyol from the viewpoint of achieving even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, abrasion resistance, and weather resistance.

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

As the carbonic acid ester, for example, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like can be used. These compounds may be used alone or in combination of two or more.

Examples of the compound having two or more hydroxyl groups include 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, 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, neopentyl glycol, trimethylolethane, glycerin and the like can be used. These compounds may be used alone or in combination of two or more. Among these, 1,3-propanediol, 1,4-propanediol and 1,4-propanediol are preferred because they provide even better adhesion to TPO leather, chemical resistance, suppression of gloss change during stretching, wear resistance, and weather resistance. -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methylpentanediol, and one or more selected from the group consisting of 1,10-decanediol Compounds are preferably used, more preferably 1,6-hexanediol.

The amount of the polycarbonate polyol used is the same as the amount of the polyol (a2), because it provides better adhesion to TPO leather, suppression of gloss change during stretching, chemical resistance, abrasion resistance, and weather resistance. It is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.

The number-average molecular weight of the polycarbonate polyol is, from the viewpoint of obtaining even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, mechanical strength, abrasion resistance, and weather resistance, A range of 100 to 100,000 is preferred, a range of 150 to 10,000 is more preferred, and a range of 200 to 2,500 is even more preferred. The number average molecular weight of the polycarbonate polyol is a value measured by gel permeation column chromatography (GPC).

The number-average molecular weight of the polyol (a2) other than the polycarbonate polyol is 500 to 100,000 from the viewpoint of obtaining even better adhesion to TPO leather, suppression of change in gloss during stretching, and weather resistance. is preferably in the range of 700 to 50,000, more preferably in the range of 800 to 10,000. The number average molecular weight of the polyol (a2) is the value measured by gel permeation column chromatography (GPC).

The amount of the polyol (a2) used is preferably in the range of 30 to 80% by mass, more preferably in the range of 40 to 75% by mass, and in the range of 50 to 70% by mass in the raw material of the urethane resin (A). is more preferred.

Examples of the chain extender (a3) include those having a number average molecular weight in the range of 50 to 450 (excluding the polycarbonate polyols). Specific examples include ethylenediamine, 1,2-propanediamine, 1, 6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3, Chain extenders having amino groups such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1 ,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxy A chain extender having a hydroxyl group such as diphenyl ether and trimethylolpropane can be used. These chain extenders may be used alone or in combination of two or more.

Among the above-mentioned chain extenders (a3), even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, mechanical strength, abrasion resistance, and weather resistance can be obtained. From the point of view of the above, it is preferable to use a chain extender having an amino group, more preferably piperazine and / or hydrazine, and the total amount of piperazine and hydrazine is 30% by mass or more in the chain extender (a3). is preferable, 50% by mass or more is more preferable, 60% by mass or more is still more preferable, and 80% by mass or more is particularly preferable. The chain extender (a3) preferably has an average functional group number of less than 3, more preferably less than 2.5. Also,

The amount of the chain extender (a3) used is such that even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, mechanical strength, abrasion resistance, and weather resistance can be obtained. From that point, it is preferably in the range of 0.5 to 10% by mass in the raw material of the urethane resin (A), more preferably in the range of 0.7 to 5% by mass, and further in the range of 0.9 to 2.3%. preferable.

As a method for producing the urethane resin (A), for example, the polyisocyanate (a1), the polyol (a2), and the raw materials used for producing the urethane resin having a hydrophilic group are reacted to obtain an isocyanate group. and then reacting the urethane prepolymer with the chain extender (a3); the polyisocyanate (a1), the polyol (a2), a hydrophilic group A raw material used for producing a urethane resin having and a method of reacting the chain extender (a3) at once. These reactions are carried out, for example, at 50 to 100° C. for 3 to 10 hours.

The sum of the hydroxyl groups of the raw material used for producing the urethane resin having a hydrophilic group, the hydroxyl groups of the polyol (a2), and the hydroxyl groups and amino groups of the chain extender (a3), and the polyisocyanate The molar ratio [(isocyanate group) / (hydroxyl group and amino group)] with the isocyanate group of (a1) is preferably in the range of 0.8 to 1.2, and 0.9 to 1.1. A range is more preferred.

When producing the urethane resin (A), it is preferable to deactivate the isocyanate groups remaining in the urethane resin (A). When deactivating the isocyanate group, it is preferable to use an alcohol having one hydroxyl group, such as methanol. The amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the urethane resin (A).

Moreover, when manufacturing the said urethane resin (A), you may use an organic solvent. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetic ester compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is finally removed by a distillation method or the like.

The content of the urethane bond in the urethane resin (A) is selected from the viewpoint of achieving even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, abrasion resistance, and weather resistance. , preferably in the range of 980 to 4,000 mmol/kg, 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, and 1,150 to 2,500 mmol /kg range. The urethane bond content of the urethane resin (A) includes the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender (a3 ) shows the value calculated from the charged amount.

The content of the urea bond in the urethane resin (A) is selected from the viewpoint of obtaining even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, abrasion resistance, and weather resistance. , preferably in the range of 315 to 850 mmol/kg, more preferably in the range of 350 to 830 mmol/kg, still more preferably in the range of 400 to 800 mmol/kg, even more preferably in the range of 410 to 770 mmol/kg. The urea bond content of the urethane resin (A) is determined by the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain extender. The value calculated from the charge amount of (a3) is shown.

The content of the alicyclic structure in the urethane resin (A) is such that even better adhesion to TPO leather, suppression of change in gloss during stretching, chemical resistance, abrasion resistance, and weather resistance can be obtained. , the range is preferably 500 to 3,000 mmol/kg, more preferably 600 to 2,900 mmol/kg, and even more preferably 700 to 2,700 mmol/kg. In addition, the content of the alicyclic structure of the urethane resin (A) is determined by the polyisocyanate (a1), the polyol (a2), the raw materials used for producing the urethane resin having a hydrophilic group, and the chain elongation The value calculated from the charged amount of the agent (a3) is shown.

The content (solid content) of the urethane resin (A) is 6 to 30% by mass in the primer layer-forming resin composition from the viewpoint of adhesion to TPO leather, coatability, workability and storage stability. is preferably in the range of , more preferably in the range of 8 to 25% by mass.

As the olefin resin (B), for example, polyolefin obtained by polymerizing a polyolefin compound; natural rubber, ethylene-vinyl acetate copolymer, synthetic isopropylene rubber; modified products thereof and the like can be used. These olefin resins may be used alone or in combination of two or more.

Examples of polyolefin compounds that can be used include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene. Moreover, these olefin compounds may be used alone or in combination of two or more. Said polyolefins may be homopolymers or copolymers.

Examples of the modified polyolefin include hydroxyl-modified polyolefin, acid-modified polyolefin, and amino-modified polyolefin. These polyolefins may be used alone or in combination of two or more. Among these, it is preferable to use an acid-modified polyolefin because it can further improve the adhesion to the TPO leather.

As the acid-modified polyolefin, for example, polyolefin modified with acid without chlorination can be used. For the acid modification, a method of reacting polyolefin with an unsaturated carboxylic acid or an anhydride thereof is preferable. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, and crotonic acid; anhydrides thereof; half esters of unsaturated carboxylic acids; , half amides, etc. can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.

Further, as the acid-modified polyolefin, it is preferable to use one having a polyether chain from the viewpoint of excellent dispersibility in water, and the polyether chain is a polyethylene chain and / or polypropylene. Chains are preferred, and polyethylene chains are more preferred.

The weight average molecular weight of the olefin resin (B) is preferably in the range of 10,000 to 500,000 from the viewpoint of obtaining even better adhesion to TPO leather and ethanol resistance. A range of 20,000 to 200,000 is more preferred. The weight average molecular weight of the olefin resin (B) is the value measured by gel permeation column chromatography (GPC).

The content (solid content) of the olefin resin (B) is from 0.5 to 0.5 in the resin composition for forming the primer layer from the viewpoint of obtaining even better adhesion to TPO leather and ethanol resistance. It is preferably in the range of 30 mass %, more preferably in the range of 0.6 to 25 mass %.

In addition, the mass ratio (solid content ratio) [(A)/(B)] of the urethane resin (A) and the olefin resin (B) is determined to provide even better adhesion to TPO leather and resistance to A range of 55/45 to 98/2 is preferable, and a range of 70/30 to 97/3 is more preferable, from the viewpoint of obtaining ethanolic properties.

Examples of the filler (C) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, and alumina silicate. can be used. These fillers may be used alone or in combination of two or more.

As the silica particles, for example, dry silica, wet silica, or the like can be used. Among these, dry silica is preferable because it has a high scattering effect and widens the range of adjustment of the gloss value. The average particle size of these silica particles is preferably in the range of 2 to 14 μm, more preferably in the range of 3 to 12 μm. The average particle size of the silica particles indicates the particle size (particle size at D50 in the particle size distribution) when the integrated amount occupies 50% in the integrated particle amount curve of the particle size distribution measurement result.

As the organic beads, for example, acrylic beads, urethane beads, silicon beads, olefin beads, etc. can be used.

The content of the filler (C) is 1.5 to 10% by mass in the resin composition for forming the primer layer from the viewpoint that the gloss value of the primer layer (i) can be easily adjusted to the range specified in the present invention. A range is preferred, and a range of 2.5 to 6% by weight is more preferred.

As the water (D), ion-exchanged water, distilled water, or the like can be used. The content of water (D) is preferably in the range of 1 to 60% by mass, more preferably 10 to 50% by mass, in the primer layer-forming resin composition from the viewpoint of coatability, workability and storage stability. % range is more preferred.

The resin composition for forming a primer layer contains the urethane resin (A), the olefin resin (B), the filler (C), and the water (D) as essential components. It may contain other additives.

Examples of other additives include cross-linking agents (E), emulsifiers, antifoaming agents, leveling agents, thickening agents, viscoelasticity modifiers, wetting agents, dispersing agents, preservatives, plasticizers, penetrating agents, and perfumes. , bactericides, acaricides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments, co-solvents, and the like can be used. These additives may be used alone or in combination of two or more.

The cross-linking agent (E) is used to improve chemical resistance, abrasion resistance, and peel strength. agents and the like can be used. These cross-linking agents may be used alone or in combination of two or more. Among these, it is preferable to use a carbodiimide cross-linking agent because it can further improve chemical resistance and peel strength.

When the crosslinking agent (E) is used, the amount used is preferably in the range of 0.1 to 5% by mass (as solid content) in the resin composition for forming the primer layer, and is preferably in the range of 0.3 to 3% by mass. more preferred.

The gloss value of the primer layer (i) is essential to be less than 0.9, more preferably in the range of 0.3 to 0.8, from the viewpoint of suppressing gloss change during stretching of the surface treatment layer. When the gloss value is within such a range, even if the thickness of the top coat is reduced during stretching of the surface treatment layer and the amount of light transmitted increases, the primer layer diffusely reflects the light, so that the gloss change during stretching of the surface treatment layer can be suppressed. guessed.

The topcoat layer (ii) contains a urethane resin (X) and beads (Y) from the viewpoint of excellent ethanol resistance and suppression of gloss change during stretching of the surface treatment layer, and furthermore, the topcoat It is essential that the filling rate of the beads (Y) in layer (ii) is in the range of 25-90%.

As the urethane resin (X), the same urethane resin (A) as used in the primer layer (i) can be used, and even better adhesion and affinity with TPO leather can be obtained. In view of this, it is preferable that the urethane resins (A) and (X) are the same material.

The content (solid content) of the urethane resin (X) is selected from the viewpoints of adhesion with TPO leather, suppression of gloss change during stretching of the surface treatment layer, coatability, workability and storage stability. It is preferably in the range of 6 to 25% by mass, more preferably in the range of 10 to 20% by mass in the resin composition for formation.

As the beads (Y), for example, acrylic beads, urethane beads, acrylic urethane beads, silicon beads, olefin beads, etc. can be used. These organic beads may be used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of acrylic beads, urethane beads, and acrylic urethane beads, since more excellent suppression of gloss change during stretching of the surface treatment layer can be obtained.

The average particle size of the beads (Y) is preferably 7 μm or more, and more preferably in the range of 8 to 15 μm, from the viewpoint of achieving even better suppression of change in gloss during stretching of the surface treatment layer. The average particle diameter of the beads (Y) is obtained by observing the beads (Y) with a scanning electron microscope and taking the diameter of a circle equal to the projected area of each of 100 particles present in a certain area as the particle diameter. It shows what was calculated by the method of finding and then averaging this.

As for the content of the beads (Y), the filling rate of the beads (Y) in the topcoat layer (ii) is preferable because it is possible to obtain even better suppression of change in glossiness during stretching of the surface treatment layer. From the viewpoint of ease of adjusting the range, it is preferably in the range of 1.5 to 30% by mass, more preferably in the range of 2 to 25% by mass in the resin composition for forming the topcoat layer.

As the water (Z), the same water (D) as used in the topcoat layer (ii) can be used. The content of water (Z) is, for example, in the range of 1 to 60% by mass in the topcoat layer-forming resin composition.

The topcoat layer (ii) contains the urethane resin (X), the beads (Y), and the water (Z) as essential components, and may contain other additives as necessary. good too.

Examples of other additives include cross-linking agents (S), fillers (T), emulsifiers, antifoaming agents, leveling agents, thickeners, viscoelasticity modifiers, wetting agents, dispersants, preservatives, and plasticizers. , penetrants, perfumes, bactericides, acaricides, fungicides, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments, co-solvents, and the like can be used. These additives may be used alone or in combination of two or more.

The cross-linking agent (S) is used to improve chemical resistance, abrasion resistance, and light resistance. Specifically, the cross-linking agent (S) that can be used in the primer layer (i) The same one as E) can be used. Among these, it is preferable to use an oxazoline cross-linking agent (OXZ) and a carbodiimide cross-linking agent (NCN) in combination from the viewpoint of achieving even better ethanol resistance and suppression of gloss change during stretching of the surface treatment layer. The ratio [OXZ/NCN] is preferably in the range of 90/10 to 20/80, more preferably in the range of 80/20 to 30/70.

When the crosslinking agent (S) is used, the amount used is preferably in the range of 0.1 to 5% by mass (as solid content) in the resin composition for forming the topcoat layer, and in the range of 0.2 to 4% by mass. is more preferred.

The filler (T) is used to adjust the gloss and improve the texture. Specifically, the same filler (C) that can be used in the primer layer (i) is used. can be used.

When the filler (T) is used, the amount used is, for example, preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.2 to 10% by mass, based on the resin composition for forming the topcoat layer.

The filling rate of the beads (Y) in the topcoat layer (ii) is in the range of 25 to 90% from the viewpoint of obtaining excellent ethanol resistance and suppression of gloss change during stretching of the surface treatment layer. is essential, and a range of 28 to 75% is more preferable. If it is in such a range, various physical properties and moldability are ensured, so it is presumed that excellent ethanol resistance and gloss change suppression during stretching of the surface treatment layer can be obtained. In addition, the filling rate of the beads (Y) in the topcoat layer (ii) indicates a value calculated by the following formula.

Calculation method of bead packing ratio for close-packed model

上記計算式により、求められた最密充填時のＰＶＣの値となる配合を１００％ビーズ充填率として、ビーズ（Ｙ）の充填率比率を求めた。

By the above formula, the filling ratio of the beads (Y) was obtained by setting the mixture that gives the value of PVC at the time of closest packing to be 100% bead filling.

Next, the surface treatment layer of the present invention will be explained.

The surface treatment layer has the primer layer (i) and the topcoat layer (ii).

As a method for producing the surface treatment layer, for example, the primer layer-forming resin composition is applied onto a substrate, dried, and then the topcoat layer-forming resin composition (ii) is applied thereon. There are methods of working and drying.

The thickness of the primer layer (i) is, for example, in the range of 2 to 30 μm, and the thickness of the topcoat layer (ii) is, for example, in the range of 2 to 30 μm.

Examples of the base material include synthetic leather, polyvinyl chloride (PVC) leather, thermoplastic olefin resin (TPO) leather, dashboards, and instrument panels. Moreover, since the surface treatment layer of the present invention has particularly excellent adhesion to TPO leather, it can be suitably used as a surface treatment agent for TPO leather.

As described above, the surface-treated layer of the present invention is environmentally friendly because it uses a material containing water, exhibits little change in gloss during stretching, and is excellent in peel strength and ethanol resistance. In particular, the surface treatment layer of the present invention is excellent in peel strength (adhesion) to TPO leather.

The present invention will be described in more detail below using examples.

[Synthesis Example 1] Preparation of aqueous dispersion of urethane resin (A-1) 250 parts by mass of methyl ethyl ketone and 0.001 mass of stannous octoate were added to a four-necked flask equipped with a stirrer, thermometer, and nitrogen reflux tube. parts, followed by 200 parts by mass of polycarbonate polyol-1 (made from 1,4-butanediol and 1,6-hexanediol, number average molecular weight: 1,000), 2,2-dimethylolpropionic acid 15 parts by mass, 49 parts by mass of isophorone diisocyanate, and 34 parts by mass of hexamethylene diisocyanate were added and reacted at 70° C. for 1 hour to obtain a methyl ethyl ketone solution of urethane prepolymer.
Next, after mixing 6.8 parts by mass of hydrazine and 15 parts by mass of triethylamine into the methyl ethyl ketone solution of the urethane prepolymer, 820 parts by mass of ion-exchanged water was added to emulsify the urethane resin (A-1) dispersed in water. I got the liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was added to obtain an aqueous dispersion of urethane resin (A-1) having a nonvolatile content of 30% by mass.
The resulting urethane 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 dispersion of urethane resin (A-2) 250 parts by mass of methyl ethyl ketone and 0.001 mass of stannous octoate were added to a four-necked flask equipped with a stirrer, thermometer, and nitrogen reflux tube. Then, 220 parts by mass of polycarbonate polyol-3 (made from 1,6-hexanediol, number average molecular weight: 2,000), 12 parts by mass of 2,2-dimethylolpropionic acid, dicyclohexylmethane 70 parts by mass of diisocyanate was added and reacted at 70° C. for 1 hour to obtain a methyl ethyl ketone solution of urethane prepolymer.
Next, after mixing 4.5 parts by mass of piperazine and 9 parts by mass of triethylamine with the methyl ethyl ketone solution of the urethane prepolymer, 880 parts by mass of ion-exchanged water was added to emulsify the urethane resin (A-2) dispersed in water. I got the liquid.
Next, methyl ethyl ketone was distilled off from the emulsion, and ion-exchanged water was added to obtain an aqueous dispersion of urethane resin (A-2) having a non-volatile content of 32% by mass.
The urethane bond content of the obtained urethane resin (A-2) was 1,278 mmol/kg, the urea bond content was 435 mmol/kg, and the alicyclic structure content was 1,713 mmol/kg.

[Preparation Example 1] Preparation of primer layer-forming resin composition (i-1) 38 parts by mass of the urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, acid-modified non-chlorinated polyolefin resin, "Arrowbase SD-1010" manufactured by Unitika Ltd., non-volatile content: 20.5% by mass, 5.5 parts by mass, silica particles produced by a dry method, average particle size: 10 μm, Hereinafter, abbreviated as “silica”.”) 3.9 parts by mass, water 44.5 parts by mass, leveling agent (“BYK-342” manufactured by BYK Chemie Japan Co., Ltd.) 0.3 parts by mass, antifoaming agent (San Nopco 0.1 part by mass of "SN Deformer 777" (manufactured by Co., Ltd.) was mixed to obtain a resin composition for forming a primer layer (i-1).

[Preparation Example 2] Preparation of primer layer-forming resin composition (i-2) In Preparation Example 1, the urethane resin (A-1) water dispersion was changed to the urethane resin (A-2) water dispersion. A primer layer-forming resin composition (i-2) was obtained in the same manner as in Preparation Example 1, except that

[Comparative Preparation Example 1] Preparation of Primer Layer-Forming Resin Composition (iR-1) F. A primer layer-forming resin composition (iR-1) was obtained in the same manner as in Preparation Example 1, except that the amount of the olefin resin used was changed from 5.5 parts by mass to 0 parts by mass.

[Comparative Preparation Example 2] Preparation of Primer Layer-Forming Resin Composition (iR-2) F. A resin composition for forming a primer layer (iR-February) was obtained in the same manner as in Preparation Example 1, except that the amount of silica used was changed from 3.9 parts by mass to 3.3 parts by mass.

[Preparation Example 3] Preparation of topcoat layer-forming resin composition (ii-1) 48.15 parts by mass of urethane resin (A-1) aqueous dispersion obtained in Synthesis Example 1, urethane beads (Negami Kogyo Co., Ltd. "ART PEARL C-600T", average particle size; ADEKA Co., Ltd. "UH-420") 2.6 parts by mass, leveling agent (BYK-Chemie Japan Co., Ltd. "BYK-342") 0.2 parts by mass, antifoaming agent (San Nopco Co., Ltd. "SN Deformer 777" ) to obtain a topcoat layer-forming resin composition (ii-1).

[Preparation Example 4] Preparation of topcoat layer-forming resin composition (ii-2) .33 parts by mass to 3.97 parts by mass, the amount of water used was changed from 34.59 parts by mass to 35.55 parts by mass, and the amount of thickener used was changed from 2.6 parts by mass to 3.2 parts by mass. A topcoat layer-forming resin composition (ii-2) was obtained in the same manner as in Preparation Example 3, except that

[Preparation Example 5] Preparation of Topcoat Layer-Forming Resin Composition (ii-3) .33 parts by mass to 0.47 parts by mass, the amount of water used was changed from 34.59 parts by mass to 23.78 parts by mass, and the amount of thickener used was changed from 2.6 parts by mass to 2.5 parts by mass. A topcoat layer-forming resin composition (ii-3) was obtained in the same manner as in Preparation Example 3, except that

[Preparation Example 6] Preparation of topcoat layer-forming composition (ii-4) A topcoat layer-forming composition (ii-4) was obtained in the same manner as in Preparation Example 3, except that

[Comparative Preparation Example 3] Preparation of Topcoat Layer-Forming Resin Composition (iiR-1) A topcoat layer-forming resin composition ( iiR-1) was obtained.

[Comparative Preparation Example 4] Preparation of Topcoat Layer-Forming Resin Composition (iiR-2) The topcoat layer-forming resin composition ( iiR-2) was obtained.

[Example 1]
To 100 parts by mass of the primer layer-forming resin composition (i-1) obtained in Preparation Example 1, a carbodiimide cross-linking agent ("Carbodilite SV-02" manufactured by Nisshinbo Chemical Co., Ltd., active ingredient: 40% by mass, carbodiimide equivalent ; 430, hereinafter abbreviated as “NCN”). Using a bar coater, the mixture was coated on a TPO leather sheet so that the wet film thickness was 30 μm, and dried at 120° C. for 1 minute to obtain a primer layer.
Next, in 100 parts by mass of the topcoat layer-forming resin composition (ii-1) obtained in Preparation Example 3, 1 part by mass of NCN, an oxazoline cross-linking agent (“Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd., active ingredient; 39% by mass, oxazoline equivalent: 220, hereinafter abbreviated as “OXZ”), 1 part by mass. The composition was applied on the primer layer using a bar coater so that the wet film thickness was 30 μm, dried at 120° C. for 1 minute to obtain a top coat layer, and an article was obtained.

[Example 2]
An article was obtained in the same manner as in Example 1, except that the NCN and OXZ used in the topcoat layer were each changed from 1 part by mass to 1.5 parts by mass.

[Example 3]
An article was obtained in the same manner as in Example 1, except that the amount of the NCN used in the primer layer was changed from 2 parts by mass to 2.5 parts by mass.

[Example 4]
In Example 1, the same as Example 1 except that the topcoat layer-forming resin composition (ii-1) used for the topcoat layer was changed to the topcoat layer-forming resin composition (ii-2). and got the goods.

[Example 5]
In Example 1, the same as in Example 1 except that the topcoat layer-forming resin composition (ii-1) used for the topcoat layer was changed to the topcoat layer-forming resin composition (ii-3). and got the goods.

[Example 6]
In Example 1, the primer layer-forming resin composition (i-1) used for the primer layer was changed to the primer layer-forming resin composition (i-2), and the topcoat layer-forming resin composition used for the topcoat layer was An article was obtained in the same manner as in Example 1, except that the resin composition (ii-1) was changed to the topcoat layer-forming resin composition (ii-4).

[Comparative Example 1]
In Example 1, the same as in Example 1 except that the primer layer-forming resin composition (i-1) used for the primer layer was changed to the primer layer-forming resin composition (iR-1). and got the goods.

[Comparative Example 2]
In Example 1, the same as in Example 1 except that the primer layer-forming resin composition (i-1) used for the primer layer was changed to the primer layer-forming resin composition (iR-2). and got the goods.

[Comparative Example 3]
In Example 1, except that the topcoat layer-forming resin composition (ii-1) used for the topcoat layer was changed to the topcoat layer-forming resin composition (iiR-1), An article was obtained in the same manner as in 1.

[Comparative Example 4]
In Example 1, except that the topcoat layer-forming resin composition (ii-1) used for the topcoat layer was changed to the topcoat layer-forming resin composition (iiR-2), An article was obtained in the same manner as in 1.

[Method for measuring number average molecular weight]
The number-average molecular weight of polyols and the weight-average molecular weight of olefin resins used in Synthesis Examples and the like are values measured under the following conditions by gel permeation column chromatography (GPC).

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8 mm I.D. x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was created using the following standard polystyrene.

(standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

[Method for measuring gloss value of primer layer (i)]
The prepared liquid for forming a primer layer was coated on black art paper with a bar coater No. 1 manufactured by Daiichi Rika Co., Ltd. 14 is used so that the wet film thickness is approximately 30 μm. After that, it is dried in a hot air dryer set at 120°C for 1 minute.
After being removed from the dryer and cooled to room temperature, the 60° specular gloss of the coated surface was measured using a specular gloss meter "Microtree Gloss" manufactured by Big Gardner.

[Method for evaluating gloss change during stretching]
The resulting article was molded using a vacuum molding machine so as to have a stretch ratio of 300%, and the appearance before and after molding was observed, and the 60 degree gloss value was measured with "Micro Tree Gloss" manufactured by Big Gardner. ” and evaluated as follows.
(exterior)
"◯": No abnormalities were observed in appearance.
"x"; Whitening or cracking of the coating film is confirmed.
(60 degree gloss value)
"Good"; Change in gloss is less than 0.5.
"Δ"; change in gloss is 0.5 or more and less than 0.8.
"x"; gloss change is 0.8 or more.

[Method for evaluating peel strength]
The surface of the obtained article was subjected to a T-shaped peel test using Tensilon (manufactured by A&D Co., Ltd.) to measure the peel strength (N/15 mm) between the surface treatment layer and the TPO leather. , was evaluated as follows. In addition, molding was performed using a vacuum molding machine so that the stretch ratio was 150%, and the peel strength (N/15 mm) of the stretched article was similarly measured and evaluated as follows.
"A"; 20 or more.
"◯"; 10 or more and less than 20;
"x"; less than 10.

[Evaluation method for ethanol resistance]
For the resulting article surface, using a Gakushin friction tester ("RT-200" manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) under a load of 500 g, the coating film surface is rubbed with a cotton cloth immersed in a 30% by mass ethanol aqueous solution. Then, the state of the coating film was observed and evaluated as follows.
"◯": No peeling of the coating film was observed after 300 cycles or more.
"X": Peeling of the coating film was confirmed after less than 300 times.

It was found that the surface treatment layer of the present invention, which uses a material containing water, has little change in gloss during stretching and is excellent in peel strength and ethanol resistance.

On the other hand, Comparative Example 1, in which the primer layer (i) did not contain the olefin resin (B), was poor in peel strength from TPO leather and ethanol resistance.

Comparative Example 2 is an embodiment in which the gloss value of the primer layer (i) exceeds the range specified in the present invention, but the change in gloss during stretching was remarkable.

Comparative Example 3 is an aspect in which the filling rate of the beads (Y) in the topcoat layer (ii) is lower than the range specified in the present invention, but the change in gloss during stretching was remarkable.

Comparative Example 3 is an aspect in which the filling rate of the beads (Y) in the topcoat layer (ii) exceeds the range defined by the present invention, but the ethanol resistance was poor.

Claims (5)

A surface treatment layer having a primer layer (i) and a topcoat layer (ii),
The primer layer (i) is formed from a primer layer-forming resin composition containing a urethane resin (A), an olefin resin (B), a filler (C), and water (D), and The primer layer (i) has a gloss value of less than 0.9,
The topcoat layer (ii) is formed from a topcoat layer-forming resin composition containing a urethane resin (X), beads (Y), and water (Z), and the topcoat layer ( A surface treatment layer characterized in that the filling rate of the beads (Y) in ii) is in the range of 25 to 90%. 2. The surface treatment layer according to claim 1, wherein the content of said filler (C) in said primer layer-forming resin composition is in the range of 1.5 to 10% by mass. 3. The surface treatment layer according to claim 1, wherein the beads (Y) in the topcoat layer-forming resin composition have an average particle size of 7 [mu]m or more. The surface treatment layer according to any one of claims 1 to 3, wherein the content of the beads (Y) in the topcoat layer-forming resin composition is in the range of 1.5 to 30 mass%. An article comprising a thermoplastic olefin resin substrate and the surface treatment layer according to any one of claims 1 to 4.