JP2007204541A - Coated form and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such a coated form that coating film including Japanese lacquer layer is industrially, swiftly and stably formed on a polyolefin resin substrate widely used in e.g. automobile internal trimmings, and to provide a method for producing the coated form. <P>SOLUTION: The coated form is such that a polyolefin resin substrate is furnished with an undercoating layer comprising a chlorinated polyolefin resin and a compounding agent(e.g. a filler), a Japanese lacquer layer and, as necessary, a topcoating layer in this order. The method for producing the coated form is also provided. In this method, it is preferable that an undercoating be dried at 40-80°C for 10-60 min, the Japanese lacquer coating at 40-60°C and 70-90% RH for 3-5 h, and the topcoating at 40-100°C for 10-60 min. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coated body in which a coating film containing a lacquer layer is provided on a polyolefin resin base material frequently used in automobile interiors and the like by an industrial method, and a method for producing the same.

The use of lacquer for automobile interiors is a long-standing hope because of the high-quality feeling of the coating film. However, it satisfies various physical properties for automobile interior due to its low weather resistance (discoloration due to light, water, etc.), poor dryness (more than 24 hours using lacquer room), lacquer rash, etc. Things are considered difficult. Another problem is that the lacquer coating film itself does not adhere to automobile substrates such as plastic.
In the conventional technology, there are those that ensure adhesion by applying a lacquer coating after applying an undercoat layer on plastic, etc., but it is still possible to improve the weather resistance, dryness, rash, etc. of lacquer. Absent. Moreover, although there exist some which mix | blend a two-component polyurethane paint etc. with a lacquer and improve drying property and a lacquer rash, a coating-film external appearance and a physical property will become a thing different from a lacquer (refer patent documents 1 and 2). ).
Japanese Patent Laid-Open No. 3-127668 JP 2002-59497 A

  An object of the present invention is to provide a coated body in which a coating film including a lacquer layer is industrially rapidly and stably formed on a polyolefin resin base material frequently used in automobile interiors and the like, and a method for producing the same. is there.

In order to achieve the above-mentioned object, the present inventor has intensively studied, and as a result, after forming an undercoat layer containing a chlorinated polyolefin resin and a compounding agent on a polyolefin resin base material, a lacquer coating is applied and the temperature and humidity are constant. It was found that the above-mentioned problems can be solved by forming a lacquer layer by applying a top coat layer and applying an overcoat layer as necessary.
That is, the present invention includes the following (1) to (7).
(1) A coated body comprising an undercoat layer composed of a chlorinated polyolefin resin and a compounding agent and a lacquer layer in this order on a polyolefin resin substrate.
(2) A coated body comprising an undercoat layer comprising a chlorinated polyolefin resin and a filler, a lacquer layer, and an overcoat layer in this order on a polyolefin resin substrate.
(3) The coated body according to (1) or (2), wherein the compounding agent is one or more inorganic fillers selected from the group consisting of silica, talc and calcium carbonate.
(4) Any of the above (1) to (3), wherein the lacquer layer is a lacquer layer formed from one or a mixture of two or more selected from the group consisting of raw lacquer, transparent lacquer, and black lacquer Painted body.
(5) The coated body according to (2), wherein the topcoat layer is a topcoat layer made of an acrylic urethane resin.
(6) The method for producing a coated body according to the above (1), wherein an undercoat paint containing a chlorinated polyolefin resin and a compounding agent is applied on a polyolefin resin substrate, and is applied at 40 to 80 ° C. It is dried for 60 minutes to form an undercoat layer, and then a lacquer coating is applied on the undercoat layer and dried at 40 to 60 ° C. and 70 to 90% RH for 3 to 5 hours to form a lacquer layer. Said method.
(7) The method for producing a coated body according to (2) above, wherein an undercoat paint containing a chlorinated polyolefin resin and a compounding agent is applied onto a polyolefin resin substrate, and the coating is applied at 40 to 80 ° C. It is dried for 60 minutes to form an undercoat layer, and then a lacquer coating is applied on the undercoat layer, dried at 40 to 60 ° C. and 70 to 90% RH for 3 to 5 hours to form a lacquer layer, and further the lacquer The method according to claim 1, wherein a top coat is applied on the layer and dried at 40 to 100 ° C. for 10 to 60 minutes to form a top coat layer.

  According to the present invention, for the first time, a lacquer coating can be applied to a polyolefin-based resin base material to which lacquer does not adhere, and a lacquer layer formed by drying stably in a short time while preventing lacquer rash, and its A manufacturing method can be provided.

Hereinafter, the present invention will be described in detail.
The chlorinated polyolefin resin for forming the undercoat layer in the present invention is a chlorinated polymer resin having a modified or unmodified polyolefin as a main skeleton. Polyolefin of the main skeleton is modified polyolefin resin modified with unsaturated dibasic acid such as maleic anhydride, hydroxyl group, carboxyl group, methacryloyl group, in addition to polyolefin (unmodified) such as polyethylene and polypropylene. Examples thereof include polyolefin-based polymers having (modified) acryloyl groups, epoxy groups and the like in the molecular ends or molecular chains.
The acrylic-modified chlorinated polyolefin resin is a modified polyolefin including a chlorinated polyolefin portion and an acrylic polymer chain portion grafted on the chlorinated polyolefin portion.
The modified chlorinated polyolefin resin is obtained by graft polymerization of a radical polymerizable monomer or copolymerization of a radical polymerizable monomer in the presence of the chlorinated polyolefin resin. The radical polymerizable monomer is not particularly limited as long as it has a radical polymerizable ethylenically unsaturated bond (—C═C—), and conventionally known esters of acrylic acid or methacrylic acid (for example, (meta ) Acrylic acid methyl, ethyl, propyl, butyl ester, etc.), unsaturated carboxylic acid (eg (meth) acrylic acid etc.), hydroxyl group-containing monomer (hydroxylethyl (meth) acrylate etc.), glycidyl group-containing monomer (Glycidyl (meth) acrylate etc.) etc. are used.
Among these, a modified polyolefin resin modified with an unsaturated dibasic acid and a modified polyolefin resin modified with maleic anhydride are preferred.
The chlorination rate of the chlorinated polyolefin resin is preferably 10 to 40% by mass, more preferably 20 to 30% by mass.
When the chlorination rate exceeds 50% by mass, the adhesion to the polyolefin resin substrate is deteriorated, and when the chlorination rate is less than 10% by mass, the solubility in the solvent is reduced and storage is performed. There is a problem with stability.
The weight average molecular weight of the chlorinated polyolefin resin is preferably 20,000 to 40,000. When the weight average molecular weight is less than 20,000, the solvent resistance is deteriorated, and when it exceeds 40,000, the solubility with the solvent is lowered, so that the storage stability is problematic.
The chlorinated polyolefin resin is commercially available. Specifically, for example, Super Clon 773H, Super Clone 822, Super Clone 892L, Super Clone 832L, Super Clone E (above, Nippon Paper Chemicals Co., Ltd.), Hardren 14LLB, Hardren CY9122, Hardren HM-21, Hardren 13-MLJ (above, manufactured by Toyo Kasei Co., Ltd.) and the like.
Any of these may be used alone or in admixture of two or more.

Examples of the compounding agent for forming the undercoat layer in the present invention include inorganic fillers such as silica, talc and calcium carbonate, organic fillers such as acrylic resin, ketone resin and polyester resin, and plastics such as polyethylene wax. Agents. Any of these may be used alone or in admixture of two or more.
Of these, one or more inorganic fillers selected from the group consisting of inorganic fillers, silica, talc and calcium carbonate are preferable, and those having an average particle diameter of 0.01 to 50 μm are particularly preferable.

  In the undercoat layer in the present invention, the compounding agent is preferably used in an amount of 1 to 100 parts by mass, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the chlorinated polyolefin resin.

In the undercoat layer of the present invention, the coating thickness obtained by dissolving and dispersing the chlorinated polyolefin resin and the compounding agent in an organic solvent (if necessary) is 1 to 100 μm, and further 10 to 40 μm. It can be suitably formed by coating on a polyolefin resin substrate and drying (or curing) at 40 to 80 ° C., particularly 50 to 70 ° C., for 10 to 60 minutes, particularly 20 to 40 minutes.
In addition, as an organic solvent which can be used as needed, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as n-propanol and n-butanol, and ester solvents such as ethyl acetate and butyl acetate. A solvent, a ketone solvent, an acetate solvent, and a mixed solvent of two or more of these can be exemplified.

As the lacquer for forming the lacquer layer in the present invention, for example, raw lacquer such as Uesuri lacquer, ground lacquer, wiping lacquer, submarine lacquer lacquer, Kijiro lacquer, lacquered lacquer, pear lacquer, Shunkei lacquer, reservoir Transparent lacquer such as lacquer, translucent coating lacquer, translucent under lacquer, black lacquer such as Ruroiro lacquer, black gloss lacquer, black matte lacquer, black central lacquer, black foil lacquer.
These can be used alone or in admixture of two or more.

The lacquer layer in the present invention is a lacquer coating obtained by dissolving and dispersing lacquer in an organic solvent (if necessary) on the undercoat layer so that the dry film thickness is 10 to 50 μm, and further 20 to 40 μm. It can be suitably formed by drying (or curing) at 40 to 60 ° C. and 70 to 90% RH for 2 to 5 hours, particularly 45 to 55 ° C. and 75 to 85% RH for 3 to 5 hours. When the dry film thickness is less than 10 μm, the coating film strength and the coating film appearance are poor, and when it exceeds 50 μm, shrinkage and poor curing occur. Normally, lacquer needs to be dried for a day or more in a high-humidity drying room called a lacquer room, but can be cured in a shorter time than before by appropriately adjusting temperature and humidity. If the humidity is too low, the curing time will be delayed, and if it is too high, shrinkage (wrinkle) and glossiness of the coating will occur. If the temperature is too low, the curing time is delayed, and if it is too high, the coating film shrinks (wrinkles) and discolors, and the curing time also becomes slow.
In addition, as an organic solvent which can be used as needed, the thing similar to what is used in formation of the said undercoat layer is mentioned.

In the present invention, an overcoat layer can be further provided on the lacquer layer, and the lacquer layer can be prevented by this overcoat layer and the lacquer layer can be protected.
Examples of the resin for forming the overcoat layer in the present invention include an acrylic resin, a polyester resin, an alkyd resin, a fluororesin, an epoxy resin, a polyurethane resin, a silicone resin, and a polyether resin. A mixture of seeds or more can be used. Among these, a polyurethane resin, and a two-component acrylic urethane resin composed of an acrylic polyol resin and a polyisocyanate curing agent are preferable.
This acrylic polyol resin has a number average molecular weight of 1,000 to 5,000, particularly 2,000 to 3,000, a hydroxyl group of 20 to 70 mgKOH / g, particularly 30 to 50 mgKOH / g, and an acid value of 1 to 5 mgKOH. / G, particularly 2 to 4 mg KOH / g is preferred. The polyisocyanate curing agent is preferably a buret, isocyanurate or adduct-modified product of hexamethylene diisocyanate having an NCO% based on the solid content of 10 to 30% by mass, particularly 15 to 25% by mass. It is preferable that the acrylic polyol resin and the polyisocyanate curing agent are mixed and used in a ratio of NCO / OH (mol ratio) of 0.7 to 1.2, and more preferably 0.9 to 1.1.

The overcoat layer in the present invention comprises a paint obtained by dissolving and dispersing the above-mentioned resin for forming an overcoat layer and optionally an additive in an organic solvent (if necessary) having a dry film thickness of 1 to 100 μm, particularly 10 to 60 μm. Thus, it can apply | coat on a lacquer layer and it can form suitably by making it dry (or harden | cure) for 10 to 60 minutes and 20 to 40 minutes at 40-100 degreeC, especially 60-80 degreeC.
Additives that can be used in combination with the formation of the overcoat layer include, in addition to pigments, wetting agents such as hydroxyl group-containing carboxylic acid esters, alkylol aminoamides, unsaturated polycarboxylic acid polyaminoamides, and polyether-modified polydimethyl Examples thereof include leveling agents such as siloxane and polyester-modified polydimethylsiloxane, and ultraviolet absorbers. Examples of pigments include organic pigments such as azo lake, phthalocyanine, indigo, perylene, quinophthalone, dioxazine, quinacridone, isoindolinone, and metal complex, and yellow lead, yellow iron oxide, bengara, and titanium dioxide. Inorganic pigments such as carbon black can be exemplified.
The additive is preferably blended so that it is contained in the resin layer (dried coating film) in an amount of 50% by mass or less, and further 0.1 to 10% by mass.
In addition, as an organic solvent used as needed, the thing similar to what is used in formation of the said undercoat layer is mentioned.

  In the present invention, the polyolefin resin base material is a modified polyolefin resin modified with an unsaturated dibasic acid such as maleic anhydride, a hydroxyl group, a carboxyl, in addition to a polyolefin (unmodified) such as polyethylene or polypropylene. A polyolefin polymer having (modified) a molecular end, methacryloyl group, acryloyl group, epoxy group, etc. in the molecular terminal or molecular chain, or an acrylic polymer chain portion grafted to these modified or unmodified polyolefin Of these, a base material made of a polyolefin, and a base material made of a polypropylene resin such as a polypropylene resin or a modified polypropylene resin is preferable.

Hereinafter, the present invention will be described in more detail with reference to examples and the like.
In the production examples, examples and comparative examples, “%” means “% by mass”.
[Preparation of paint]
Production Example 1 (Preparation of undercoat paint)
(1) Preparation of vehicle Maleic anhydride-modified chlorinated polypropylene resin (solid content 20%), silica, talc, and toluene are mixed and dissolved at 75/2/8/15 (mass ratio) to prepare a vehicle. did.
(2) Preparation of undercoat paint The above-mentioned vehicle and an organic solvent (toluene / xylene = 80/20 (mass ratio)) are blended at 100/120 (mass ratio) and mixed to prepare an undercoat paint with a desired viscosity. Prepared.

Production Example 2 (Preparation of lacquer paint)
Pure wax-colored black lacquer and toluene were blended at 40/60 (mass ratio) and mixed to prepare a lacquer paint having a desired viscosity.

Production Example 3 (Preparation of top coat)
(1) Preparation of main component Acrylic polyol resin (copolymer of styrene / methyl methacrylate containing hindered amine in skeleton, solid content 60%) and organic solvent (methyl isobutyl ketone / acetylacetone = 66/34 (mass ratio)) A base material for top coating was prepared by blending additives (leveling agent and ultraviolet absorber) at 78/15/7 (mass ratio).
(2) Preparation of curing agent An isocyanate resin (isocyanurate-modified hexamethylene diisocyanate, solid content 100%) and an organic solvent (xylene / butyl acetate = 22/78 (mass ratio)) were blended at 55/45 (mass ratio). A curing agent for polyisocyanate for top coating was prepared.
(3) Preparation of coating material for top coating The main agent / curing agent / organic solvent (toluene / xylene / butyl acetate / methoacetate = 25/25/25/25 (mass ratio)) at 100/25/75 (mass ratio) The mixture was blended and mixed to prepare a paint for top coating.

[Formation of coating layer]
Example 1
(1) Formation of undercoat layer The undercoat paint prepared in Production Example 1 (2) was spray-coated on a polypropylene resin substrate so as to have a dry film thickness of 15 to 25 μm, and dried at 60 ° C. for 30 minutes. An undercoat layer was formed.
(2) Formation of lacquer layer On the surface of the undercoat layer formed in the above process, the lacquer paint prepared in Production Example 2 was applied so as to have the dry film thicknesses shown in Tables 1 to 3, and at 50 ° C and 80% RH. Dried for 4 hours.
These results are summarized in Tables 1 to 3.

Example 2
(1) Formation of undercoat layer The undercoat paint prepared in Production Example 1 (2) was spray-coated on a polypropylene resin substrate so as to have a dry film thickness of 15 to 25 μm, and dried at 60 ° C. for 30 minutes. An undercoat layer was formed.
(2) Formation of lacquer layer On the surface of the undercoat layer formed in the above step, the lacquer coating material prepared in Production Example 2 was applied so as to have a dry film thickness of 35 to 45 μm, and at 50 ° C. and 80% RH for 4 hours. Dried.
(3) Formation of topcoat layer The topcoat paint prepared in Production Example 3 was applied to the surface of the lacquer layer formed in the above step so as to have a dry film thickness of 15 to 25 µm, and dried at 80 ° C for 30 minutes.
The results are summarized in Table 4.

Comparative Example 1
On the polypropylene resin base material, the lacquer paint prepared in Production Example 2 was applied to a dry film thickness of 35 to 45 μm, and dried at 50 ° C. and 80% RH for 4 hours.
The results are summarized in Table 4.

From Table 4, the lacquer layer was able to be stably formed in the polypropylene resin base material which lacquer does not adhere in a short time. Moreover, the obtained lacquered product is excellent in water resistance, alkali resistance, acid resistance, and weather resistance, and has durability not found in conventional lacquered products.

Claims (7)

  A coated body comprising an undercoat layer comprising a chlorinated polyolefin resin and a compounding agent and a lacquer layer in this order on a polyolefin resin substrate.   A coated body comprising an undercoat layer comprising a chlorinated polyolefin resin and a filler, a lacquer layer, and an overcoat layer in this order on a polyolefin resin substrate.   The coated body according to claim 1 or 2, wherein the compounding agent is one or more inorganic fillers selected from the group consisting of silica, talc and calcium carbonate.   The coated body according to any one of claims 1 to 3, wherein the lacquer layer is a lacquer layer formed from one or a mixture of two or more selected from the group consisting of raw lacquer, transparent lacquer, and black lacquer. .   The coated body according to claim 2, wherein the topcoat layer is a topcoat layer made of an acrylic urethane resin. It is a manufacturing method of the coating object according to claim 1,
On the polyolefin resin substrate, an undercoat paint containing a chlorinated polyolefin resin and a compounding agent is applied, dried at 40 to 80 ° C. for 10 to 60 minutes to form an undercoat layer, and then on the undercoat layer The said method characterized by apply | coating a lacquer coating material and making it dry at 40-60 degreeC and 70-90% RH for 3 to 5 hours, and forming a lacquer layer. It is a manufacturing method of the coating object according to claim 2,
On the polyolefin resin substrate, an undercoat paint containing a chlorinated polyolefin resin and a compounding agent is applied, dried at 40 to 80 ° C. for 10 to 60 minutes to form an undercoat layer, and then on the undercoat layer A lacquer coating is applied, dried at 40 to 60 ° C. and 70 to 90% RH for 3 to 5 hours to form a lacquer layer, and further a top coating is applied on the lacquer layer, and 10 to 60 at 40 to 100 ° C. Drying for a minute to form an overcoat layer.