JPH07247463A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition having excellent adhesivity to substrate, water-resistance, etc., and suitable as a surface-coating material for a fluoropolymer substrate by compounding a polyurethane resin with a modified PVA containing sulfonic acid group, a crosslinking agent and organic and inorganic fillers. CONSTITUTION:This coating composition contains (A) a polyurethane resin (preferably a self-emulsifiable aqueous polyurethane), (B) a modified PVA containing sulfonic acid group (preferably a PVA having a number-average molecular weight of 7,000-30,000 and a saponification degree of 40-70mol%), (C) a crosslinking agent (preferably glycerol triglycidyl ether, etc.), (D) an organic filler (preferably a styrene-acrylonitrile copolymer, etc.) and (E) an inorganic filler (preferably colloidal silica, etc.). The weight ratio of A:B is preferably 80:20 to 60:40. The amounts of the components C, D and E are 5-20 pts.wt., 5-30 pts.wt. and 1-20 pts.wt. based on 100 pts.wt. of A+B, respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to coating compositions based on polyurethane resins. More specifically, the present invention is excellent in properties such as adhesion to a substrate, water resistance, and handleability, and a coating layer formed from the coating composition of the present invention includes a water-based ink, a water-based coating, and various toners. Depending on the, etc., it has a beautiful and vivid color tone, characters and figures without blurring,
The present invention relates to a coating composition capable of printing, painting, and copying an image or the like in a short time efficiently, clearly and with good adhesion, and the coating composition of the present invention has a surface free energy. It is particularly suitable as a surface coating material for films, sheets, and other products made of a fluoropolymer having a very low affinity with most substances due to its small size.

[0002]

2. Description of the Related Art Fluoropolymers have low surface free energy, are extremely excellent in chemical resistance, stain resistance and weather resistance, do not react with many chemicals, and are insoluble in ordinary solvents. Is. Therefore, molded products such as sheets and films made of fluoropolymers and other products are inferior in adhesiveness to dyes, paints, inks, etc. on the one hand, and printing, painting, drawing, etc. must be performed without special treatment. Is extremely difficult.

Conventionally, when printing characters or patterns on the surface of a molded article such as a fluoropolymer film or sheet by printing or other methods, the surface of the fluoropolymer is hydrophilized by corona discharge treatment or the like. After that, silk printing or offset printing is generally performed using an organic solvent-based ink or paint, and a binder component such as (meth) acrylic acid-based polymer, (meth) acrylic resin, urethane resin, and celluloses. A large number of inks and paints for fluoropolymers prepared by dissolving the above in an organic solvent have been developed and are commercially available.

However, silk printing and offset printing using organic solvent-based inks and paints are not cost effective unless the number of printed sheets is large, and are not desirable as a method for forming an image on a fluoropolymer molded article. Absent. In addition, since the use of organic solvents causes deterioration of the natural environment and work environment, and there is a danger of fire, there is a strong demand for a shift to water-based paints and inks.

In recent years, vinyl chloride resin sheets, paper,
It is widely used to produce visual signs and advertisements using marking films and marking sheets made of synthetic paper, etc., but when used outdoors, it is durable, fading resistant, stain resistant, as it is. Due to poor weather resistance and the like, overlaying with a fluoropolymer film or the like, which is excellent in these properties, has been performed. However, since the fluoropolymer film has a poor affinity with vinyl chloride resin sheets, paper, etc., it is also subjected to corona discharge treatment, etc. to activate the surface and have an affinity with base materials such as vinyl chloride resin sheets. Then, a method of adhering it to the base material using an adhesive or the like is adopted.

However, in that case, drawing on a substrate such as a vinyl chloride resin sheet or paper, surface activation treatment of the fluoropolymer film, and further activation of the activated fluoropolymer film on the substrate. Since a multi-step process of sticking and many materials are required, simplification is required in terms of manufacturing process and cost.

[0007]

An object of the present invention is to use a water-based ink or a water-based paint on the surface of a fluoropolymer sheet or film, or a substrate made of other material, and an ink jet method, Characters and designs can be printed or painted by various printing methods such as spray jet method, offset printing, silk printing, gravure printing, and various coating methods. Furthermore, characters and patterns can be printed by electrostatic copying using toner. It is an object of the present invention to provide a surface coating material for a base material which is made of a fluoropolymer or other material and which enables copying of images and the like. The object of the present invention is to use the above-mentioned inks, paints, toners, etc., to provide characters, patterns, images, etc., which are excellent in characteristics such as color tone, sharpness, bleeding resistance, stain resistance, light resistance, and peel resistance. It is an object of the present invention to provide a surface coating material having excellent workability, which enables direct printing, painting, and copying on the surface of a substrate efficiently in a short time. Further, it is an object of the present invention to provide a surface coating material which, in addition to the above-mentioned excellent properties, has excellent adhesion to substrates, inks, paints, toners, etc. and also excellent water resistance.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned object. As a result, a polyurethane resin is used as a base resin, and a sulfonic acid group-containing modified polyvinyl alcohol, a crosslinking agent, an organic filler and When an inorganic filler is blended and, if necessary, an amino compound or a surfactant is further blended to form a coating composition, the workability and water resistance are excellent, and a fluorine-based polymer sheet, a film or the like is included. It is possible to obtain a coating composition having excellent adhesion to various substrates, and for the coating layer formed from this coating composition, an aqueous ink, an inkjet method using a water-based coating, a spray jet method, Adhesion and resistance by any printing method such as offset printing, silk printing, gravure printing, any painting method, and electrostatic copying method. Bleeding property, coloring property, excellent in such oil resistance (ink absorbency), vivid and beautiful color tone of the character, the symbol, such as very easily the image, and have completed the present invention found that can promptly appear.

That is, the present invention is characterized by containing a polyurethane resin (A), a sulfonic acid group-containing modified polyvinyl alcohol (B), a crosslinking agent (C), an organic filler (D) and an inorganic filler (E). And the coating composition. And the present invention includes an organic polymer product coated with the above coating composition.

As the polyurethane-based resin (A) used as the base resin in the coating composition of the present invention, any of the polyurethane-based resins usually used in polyurethane-based resin coatings can be used, and the urethane-based resin is used in the process of forming a coating film. Any of those that form a bond (-NH-CO-O-) or those that have a urethane bond in the resin beforehand can be used. Polyurethane resin for paints is a two-component type which is a combination of various polyols and polyisocyanate, moisture-curable polyurethane resin, blocked isocyanate-curable polyurethane resin, oil-modified polyurethane resin (urethane oil, urethane resin). Alkyd resin, etc.) and a one-pack type using a lacquer type polyurethane resin as a vehicle, both of which can be used in the present invention.

As the isocyanate compound for the polyurethane resin (A), any of the isocyanate compounds usually used in polyurethane resin coatings can be used. For example, tolylene diisocyanate and 4,4-
Diphenylmethane diisocyanate, Polymeric-
4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tolidine diisocyanate, tetramethylyl xylylene diisocyanate,
Aromatic diisocyanates such as 3,3′-dichloro-4,4′-diphenylmethane diisocyanate; hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, isopropylidene bis (4-
Alicyclic or aliphatic diisocyanates such as cyclohexyl diisocyanate), cyclohexyl diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate; lysine diisocyanate; dimerization products, trimerization products, and carbodiimidization products thereof. You can These organic diisocyanates may be used alone or in combination of two or more.

When a two-pack type polyurethane resin (A) is used, the above-mentioned isocyanate compound or an isocyanate resin previously prepared using the above-mentioned isocyanate compound together with a polyol (isocyanate-terminated resin) is used. ) Are used, and these polyols and isocyanate compounds or isocyanate resins are mixed immediately before coating the coating composition on the substrate to form a coating layer on the substrate by polymerizing by urethane bond formation. .

As the polyol in this case, a low molecular weight polyol and / or a high molecular weight polyol can be used. As the low molecular weight polyol, ethylene glycol, diethylene glycol, 1,4-butanediol,
Trimethylolpropane, neopentyl glycol,
1,6-hexanediol and the like, and as the polymer polyol, for example, polyethylene glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer, polyether polyol such as polytetramethylene ether glycol; poly-β-
Polyester polyol such as polyester comprising methyl-δ-valerolactone, polycaprolactone, diol and dibasic acid such as adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid; polycarbonate polyol; polyether ester polyol; acrylic Examples thereof include polyols; epoxy-based polyols; liquid butadiene having a hydroxyl group; and neoprene having a hydroxyl group. Of the above-mentioned polyols, polyester polyols are particularly preferable in that yellowing hardly occurs.

When an isocyanate resin is used as the isocyanate component, the above-mentioned isocyanate compound is added to ethylene glycol, propylene glycol, butanediol or other diols; glycerin, pentaerythritol, and other trifunctional or higher functional polyols. An isocyanate resin such as a polyisocyanate prepolymer obtained by reacting with one kind or two or more kinds, a burette or an isocyanurate type polyfunctional trimer can be used.

When a one-pack type moisture-curable polyurethane resin is used as the polyurethane resin (A),
Although a conventionally known moisture-curable polyurethane resin used as a paint can be used, this moisture-curable polyurethane resin easily reacts with the moisture in the inorganic filler (E), and thus requires careful handling.

As the polyurethane resin (A), 1
When a liquid block isocyanate-curable polyurethane resin is used, alcohol, phenol, active methylene (for example, acetoacetic acid, lactam, oxime, etc.) is added to the isocyanate compound or isocyanate resin as described above.
It is possible to use a mixture of a low molecular polyol and / or a high molecular polyol as described above, which is obtained by reacting a blocking agent such as, for example, to block and stabilize the isocyanate group.

When a one-pack type oil-modified polyurethane resin is used as the polyurethane resin (A), it is obtained by transesterifying a drying oil with a polyhydric alcohol and reacting it with the polyisocyanate compound as described above. It is possible to use a urethanized alkyd resin obtained by reacting a polyisocyanate compound with a urethanized oil or a drying oil fatty acid-modified alkyd resin. Also,
When a one-pack lacquer type polyurethane resin is used as the polyurethane resin (A), a high molecular weight diisocyanate-terminated prepolymer obtained by reacting a bifunctional polyester polyol with a diisocyanate compound is used to produce a low molecular weight glycol or amine. It is possible to use a chain extender consisting of

In the present invention, as the polyurethane resin (A), it is preferable to use an aqueous polyurethane resin among the above-mentioned various polyurethane resins from the viewpoint of workability, and particularly a self-emulsifying type resin is used. Is more preferable. In preparing the coating composition of the present invention, the polyurethane resin (A) is used in the form of liquid, solution,
It can be used in any form such as dispersed liquid form or solid form.

Sulfonic acid group-containing modified polyvinyl alcohol (hereinafter referred to as "SA modified P") used as the component (B) in the present invention.
VA (B) ”) is a polymer having a structural unit derived from a monomer having a sulfonic acid group in the main chain of polyvinyl alcohol. Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, (meth) allyl sulfonic acid, (meth) acrylamido-N-alkyl sulfonic acid and metal salts thereof, and among these, vinyl sulfonic acid Acid, (meth) allyl sulfonate,
(Meth) acrylamide-N-2-methylpropyl sulfonate is preferably used. In the present invention, as the SA-modified PVA (B), a structural unit derived from the sulfonic acid group-containing monomer is 0.1 to 5 mol% based on all the structural units of the SA-modified PVA (B). Is preferable from the viewpoint of solubility in water / organic mixed solvent, and the proportion of structural units derived from the sulfonic acid group-containing monomer is 0.3 to 2 mol%.
It is more preferable to use the one described above. In addition, SA modified P
VA (B) has a number average molecular weight of 5,000 to 1
It is preferable to use those having a saponification degree of 20,000 and a saponification degree of 10 to 80 mol% from the viewpoint of water resistance and solubility. The number average molecular weight is 7,000 to 30,000 and the saponification degree is 40 to 70.
It is more preferable to use the one of mol%.

The SA-modified PVA (B) is generally prepared by copolymerizing a vinyl alcohol ester such as vinyl acetate with a sulfonic acid group-containing monomer and then saponifying the ester group in the copolymer to convert it into an alcohol group. It can be manufactured, and its specific manufacturing method is described in, for example, JP-A-56
No. 72006, etc. But S
The method for producing the A-modified PVA (B) is not particularly limited and may be produced by any method. In addition, SA-modified PVA (B) was manufactured by Kuraray Co., Ltd. under the condition of "HM-N-0.
4 ”and the like, which may be used as they are.

In the coating composition of the present invention, the polyurethane resin (A) and the SA-modified PVA (B) are
(A) :( B) = 90: 10 to 10:90 is preferably used in a weight ratio, and more preferably 80:20 to 60:40 is used in a weight ratio. Although the SA-modified PVA (B) is heat-meltable, since it dissolves in water, the polyurethane resin (A) is used in a larger amount than the SA-modified PVA (B) from the viewpoint of the water resistance of the coating layer. Is preferred.

In the coating composition of the present invention, by using the polyurethane resin (A) in combination with the SA-modified PVA (B), the adhesion between the coating layer and the substrate,
The water resistance of the coating layer is improved, and when printing, painting or electrostatic copying is performed on the coating layer, adhesion between the coating layer and ink, paint, toner, etc., color development, bleeding resistance, oil absorption Properties (absorption rate) and other properties become extremely good. In particular, when the polyurethane resin (A) and the SA-modified PVA (B) are used in the above weight ratio, their properties can be further improved.

The SA-modified PVA used in the present invention
(B) dissolves in water, and at the same time, dissolves in a mixed solvent of water and alcohol, a mixed solvent of water and another polar solvent, and such a mixed solvent is used for the polyurethane resin (A). Since it also serves as a solvent, various solvents can be used in preparing the coating composition. On the other hand, unmodified polyvinyl alcohol containing no sulfonic acid group is soluble in water but not in a mixed solvent of water and alcohol or water and another polar solvent. Therefore, SA-modified PVA (B ) Has an advantage.

Further, the coating composition of the present invention contains a cross-linking agent (C), and the cross-linking agent (C) is a polyurethane resin (A) and SA-modified PVA (B), and further an amino compound. A polyurethane resin (A), an SA-modified PVA (B), and optionally an amino compound (F), which comprises a compound having two or more functional groups capable of reacting with (F).
To form a water-insoluble crosslinked coating layer on the substrate. Examples of the cross-linking agent (C) usable in the present invention include epoxy compounds, aldehyde compounds, aziridine compounds,
Examples thereof include aminoplast compounds and polyvalent metal compounds. In some cases, blocked polyisocyanate compounds may be used as a crosslinking agent separately from the polyurethane resin (A).

When an epoxy compound is used as the crosslinking agent (C), any compound having two or more epoxy groups represented by a glycidyl group in the molecule can be used, and specific examples include sorbitol polyglycidyl ether, Examples thereof include glycerol diglycidyl ether, glycerol triglycidyl ether, polyethylene glycol diglycidyl ether, and polyamide epichlorohydrin resin, and among these, glycerol triglycidyl ether is preferable.

When an aldehyde compound is used as the cross-linking agent (C), any compound can be used as long as it produces an aldehyde when the coating layer is formed. Specific examples include formalin, acetaldehyde, propionaldehyde and butyl. Monoaldehydes such as aldehydes, polyhydric aldehydes such as glyoxal, glutaraldehyde, and dialdehyde starch, polyaldehydes, condensates of formalin and ammonia such as hexamethylenetetramine,
Examples thereof include acrylamide glyoxal reaction copolymer, and of these, glyoxal is preferable.

When an aziridine compound is used as the cross-linking agent (C), it is preferable to use one having two or more ethyleneimine derivative groups in the molecule. As a specific example, the following formula ( 1) and the formula (2) can be mentioned.

[0028]

[Chemical 1]

[0029]

[Chemical 2]

When an aminoplast compound is used as the cross-linking agent (C), a condensate of an aldehyde with a compound having an amino group such as melamine, a urea-aldehyde complex or an aniline-aldehyde complex, or a compound thereof A methylol compound, an alkoxy compound, an alkoxymethyl compound, an amidated compound, etc. can be used. Also,
When a blocked isocyanate compound is used as the crosslinking agent (C), the same isocyanate group-blocked compound as described for the polyurethane resin (A) can be used.

The proportion of the cross-linking agent (C) used is the type of the polyurethane resin (A), the SA-modified PVA (B) and the amino compound (F) optionally used, the number of functional groups in these compounds, and the cross-linking agent ( Although it may vary depending on the type of C), the number of functional groups, etc., generally, the amount of the cross-linking agent (C) used is 0.1 part with respect to 100 parts by weight of the total amount of the polyurethane resin (A) and the SA-modified PVA (B). It is preferably from 05 to 30 parts by weight, more preferably from 5 to 20 parts by weight. In the coating composition of the present invention, by using the crosslinking agent (C), the water resistance of the coating layer formed on the base material can be significantly improved, and the adhesion between the coating layer and the base material can be improved. Also, the adhesion of the coating layer to ink, paint, toner, etc. can be improved.

Further, the coating composition of the present invention contains an organic filler (D), and this organic filler (D) has an affinity for ink, water pigment, paint, toner and coating layer (coating layer It is possible to improve the acceptability for inks, water-based pigments, paints, toners, and the like, and to enhance the color developability thereof, so that a finished state with a clear and beautiful color tone can appear. As the organic filler (D), acrylic polymer beads [preferably a thermoplastic homopolymer or copolymer mainly composed of (meth) acrylic acid ester], styrene-acrylonitrile copolymer, methyl methacrylate-
Examples thereof include butadiene-styrene copolymer, urea-formalin resin, and organic bentonite. Among these, urea-formalin resin and styrene-acrylonitrile copolymer are preferably used. When a urea-formalin resin is used as the above-mentioned cross-linking agent (C), it can serve both as a cross-linking agent (C) and an organic filler (D).

Furthermore, the coating composition of the present invention contains an inorganic filler (E), and by using the inorganic filler (E), the coating composition of the present invention for inks, water-based pigments, paints, toners and the like. It is possible to improve the acceptability and color development. As the inorganic filler (E), calcium carbonate, silica-based compounds, titanium oxide, talc, aluminum silicate, magnesium aluminosilicate, clay and the like can be used, and among these, white carbon and other silica-based compounds. Porous substances such as aluminum silicate are preferable because of their high ability to receive inks, paints, toners and the like. In particular, inorganic filler (E)
When colloidal silica is used as the material, it is desirable because it is possible to improve the ink receptivity and the color developability as well as the adhesion to the substrate and the water resistance. In the preparation of the coating composition, the inorganic filler (E) may be used as a solid powder as it is, or may be used in the form of a dispersion in which water or a solvent is dispersed, a polymer dispersion, or the like. Examples of such dispersion liquids include silica sol, alumina sol and the like dispersed in water, a solvent, an acrylic emulsion, and the like. These are, for example, by Nissan Chemical Industries, Ltd. as alumina sol-100 and aluminum sol-200, It is also sold as Alumina sol AS series by Catalysts & Chemicals Co., Ltd.

In the coating composition of the present invention, the ratio of the organic filler (D) is 0.1 to 50 relative to 100 parts by weight of the total amount of the polyurethane resin (A) and the SA-modified PVA (B).
Parts by weight, preferably 5 to 30 parts by weight, and the proportion of the inorganic filler (E) is 0.1 to 30 parts by weight, preferably 1 to
It is preferably 20 parts by weight. In that case, the weight ratio of the organic filler (D): inorganic filler (E) is 99: 1 to
1:99, preferably 95: 5 to 60:40, and {polyurethane resin (A) and SA-modified PVA
The total weight of (B)}: {total weight of organic filler (D) and inorganic filler (E)} is 10:90 to 90:
It is preferable that it is 10, preferably 80:20 to 70:30. When the proportion of the inorganic filler (E) is higher than the above, the adhesiveness to the base material, particularly the base material made of the fluoropolymer, tends to be lowered.

The coating composition of the present invention may further contain an amino compound (F) if necessary.
Examples of the amino compound (F) include polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, triaminopropane and polyethyleneimine or salts thereof, melamine resins, polyolefin-based copolymers having amino groups or salts thereof, chitosan, amino. Examples thereof include celluloses having an amino group such as group-modified cellulose or salts thereof, and amino group-modified starch or salts thereof. Among them, chitosan and polyethyleneimine are preferable, and polyethyleneimine having a molecular weight of 300 to 80,000 is preferable, and
It is more preferably -30000.

When the amino compound (F) is used,
The ratio of the amino compound (F) is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the polyurethane resin (A) and the SA-modified PVA (B). When the amino compound (F) is used together with the crosslinking agent (C), the water resistance of the coating layer formed from the coating composition of the present invention can be further improved.

Further, the coating composition of the present invention may optionally contain a surfactant (G) in order to improve the dispersibility of each of the above-mentioned components. As the surfactant (G), A conventionally known nonionic surfactant, anionic surfactant or the like can be used. Surfactant (G)
The use ratio of is preferably about 0.01 to 5% by weight based on the total weight of the coating composition of the present invention. Further, the coating composition of the present invention contains, in addition to the above-mentioned components, an antifoaming agent, an ultraviolet absorber for improving light resistance and fading resistance, an antioxidant, an antibacterial agent, etc., if necessary. You may have.

The coating composition of the present invention can be used for printing, painting, electrostatic copying, etc., using the above-mentioned ink, paint, toner and the like on the coating layer formed from the coating composition of the present invention. It is preferably used as a coating treatment material for the surface of the substrate for carrying out, but is not limited thereto, pigments, dyes, other colorants and the like are directly compounded in the coating composition of the present invention, Forming a colored layer directly on the surface of the material,
It may be used to draw characters, patterns, etc.

The coating composition of the present invention comprises water, a mixed solvent of water and alcohol, an alcohol, a polar solvent other than alcohol (for example, dimethylformamide, dimethylsulfoxide, etc.), and a mixture of water and those polar solvents. It is preferable to prepare by dispersing or dissolving each of the above components in a liquid medium such as a solvent. Particularly, water, alcohol (especially methanol) is used as a medium for solubility, safety,
It is preferable from the viewpoints of preventing air pollution and workability. In the preparation of the coating composition, when a two-component polyurethane resin or a moisture-curable polyurethane resin that reacts rapidly with water or moisture is used as the polyurethane resin (A),
Select the type of liquid medium and the time of addition of polyurethane resin (A) so that gelation and undesired side reactions due to the reaction of isocyanate groups do not occur during the preparation stage of coating compositions and during coating operations. There is a need.

The viscosity of the coating composition can be variously changed according to the kind of the substrate to be coated, etc., but in general, it is about 10 when measured by the Bruckner method at a temperature of 25 ° C.
It is preferable that the viscosity is about 900 cps from the viewpoint of workability at the time of coating, drying speed, performance of the obtained coating layer, and the like, and a viscosity of about 30 to 200 cps is more preferable. Although it may vary depending on the type of each component used, the mixing ratio, the type of liquid medium, etc., generally, the total solid content concentration in the coating composition is about 5 to 40% by weight, preferably 1
When it is about 0 to 25% by weight, the coating composition having the above-mentioned viscosity can be obtained.

The coating composition of the present invention can be used for coating various substrates, for example, substrates made of organic polymers, paper, cloth, metal, wood, etc., and the form of the substrate is a sheet, It may be in any form such as a film, a plate, a tube or a mold, but it may be a fluoropolymer, polyester, polyamide, acrylic polymer, polyurethane, polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, natural. It is also suitable for coating various plastics such as synthetic rubber and film of rubber, sheets, and other molded products. In particular, the coating composition of the present invention includes polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer. Coalesce, trifluoroethylene-tetrafluoroethylene copolymer, trifluoroethylene-tetrafluoroethylene-alkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer,
Excellent adhesion to various fluorine-based polymers such as fluorine-containing acrylic acid ester polymers, copolymers of fluorine-containing acrylic acid esters with methacrylic acid and / or methyl methacrylate, and these fluorine-based polymers Suitable for coating films, sheets and other molded products.

In coating the substrate with the coating composition of the present invention, brush coating, roller coating, spray coating,
Any coating method or coating method such as cast coating or coating (curtain flow coater coating or blade coater coating), screen coating, calendar coating or dip coating can be used. The thickness of the coating layer can be appropriately adjusted depending on the type and application of the base material, but in general, it is preferable to perform coating so that the thickness of the coating layer after drying is 3 to 100 μm. -40 μm is more preferable. The above thickness is particularly suitable when coating a film or sheet of a fluoropolymer.

The coating layer formed from the coating composition of the present invention has excellent adhesion to water-based inks, water-based paints, toners used in electrostatic copying machines, and the like, and also has color-developing property, bleeding resistance, and
Since it is also excellent in terms of oil absorption (absorption rate of ink, etc.), an ink jet method, a spray jet method using a water-based ink or a water-based paint, etc. on the coating layer formed from the coating composition of the present invention Method, offset printing method, silk printing method, gravure printing method, and any printing method, and even with an electrostatic copying machine, color development, sharpness, bleeding resistance, oil absorption (such as ink) It is possible to easily form clear characters and images with beautiful color tone, which has excellent absorption speed) and adhesion, in a short time. In particular, due to its small surface free energy, characters made with water-based ink, water-based paint, toner, etc. It has become possible to print or paint with water-based ink or water-based paint, and electrostatic copying on a substrate made of a fluoropolymer, which has been almost impossible to print or paint images.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% mean parts by weight and% by weight, respectively, unless otherwise specified. Also,
The test in each example was performed by the following method.

Adhesion test : (1) A base material (fluorine-based polymer film) is coated with a coating composition and then dried, and a cellophane tape is adhered on the coating layer formed as a result, and then the base material. Hold each of the ends of the tape and cellophane tape and peel them off at an angle of 180 degrees,
The ratio of the coating layer adhered to the adhesive surface of the cellophane tape was examined, and the adhesion between the substrate and the coating layer was evaluated according to the evaluation criteria shown in Table 1 below. (2) A base material (fluorine-based polymer film) is coated with a coating composition and then dried to form a coating layer, and a desk writer 550 (dye-based aqueous ink: manufactured by Hulett Packard) is formed on the coating layer. Draw 1 line with a thickness of 1 mm using red) in parallel with each other with a space of 1 mm, dry the ink, and then attach a cellophane tape on the surface drawn with the ink, and the end of the base material and the cellophane tape. Each of them is peeled off instantaneously at an angle of 180 degrees, and the ratio of the ink adhering to the adhesive surface of the cellophane tape is examined to determine the adhesion between the coating layer and the ink according to the evaluation criteria shown in Table 1 below. evaluated.

[0046]

[Table 1] Evaluation criteria for adhesion ⊚: There is no peeling of the coating layer or ink and the adhesion is very good. ◯: Almost no peeling of the coating layer or ink (peeling is less than 5% in area ratio), and the adhesion is good. Δ: Coating Peeling of the layer or the ink occurs in an area ratio of about 5 to 25%, and the adhesion is considerably poor. X: Peeling of the coating layer or the ink occurs in an area ratio of 50% or more, and the adhesion is poor.

Water resistance test : After coating a coating composition on a base material and drying it to form a coating layer, the coating layer was immersed in water at room temperature (25 ° C.) for 1 month and then taken out. The adhesion with the substrate was tested in the same manner as the above-mentioned adhesion test (1), and the adhesion of the coating layer was examined to evaluate the water resistance.

Color development test of ink : A base material (fluorine-based polymer film) is coated with a coating composition and then dried to form a coating layer, and a desk writer manufactured by Hulett Packard is then formed thereon. 1mm thickness of 1mm line using 550
10 lines are drawn in parallel with each other at intervals, and after the ink is dried, the state of color development is visually observed, and it is as clear as when a line is similarly drawn on the paper with the same ink. Color was evaluated as ⊚, slightly less clear but almost clear, as ◯, considerably faded color and poor clarity as Δ, and extremely fading was evaluated as x.

Ink bleeding test : In the same manner as in the ink color development test, a line is drawn on the coating layer on the substrate to visually convert the ink bleeding condition. ⊚, when there was almost no bleeding was evaluated as ◯, when there was considerable bleeding was evaluated as Δ, and when bleeding was extremely large, as x.

Measurement of oil absorption (ink absorption rate) : A substrate (fluorine polymer film) is coated with a coating composition and dried to form a coating layer, on which an aqueous inkjet ink [Komatsu A pattern was drawn by an inkjet method using "Sharing" (blue) manufactured by Smelting Co., Ltd., and the oil absorption (ink absorption rate) was measured according to JIS 8111 using a printing paper oil absorption meter manufactured by Toyo Tester. .

Copy test by electrostatic copying machine : A substrate (fluorine-based polymer film) was coated with a coating composition and then dried to form a coating layer, and the resulting substrate with the coating layer was obtained. Using as a copy paper, a color copy machine "ARTAGE-8000" manufactured by Ricoh Co., Ltd. was used to make a color copy, and the color-developed state was visually observed.
◎ when copied in the same vivid color as the original, ○ when the color tone is slightly dull than that but almost the same shade as the original ○, the color tone is considerably dull compared to the original and copied The evaluation was evaluated as Δ when the image was reproduced, and × when the image was copied because the color tone was significantly inferior to the original.

Example 1 (1) Urea-formalin resin (organic filler) (“U-Pearl” manufactured by Mitsui Toatsu Chemicals, Inc .; solid content concentration 30%)
30 parts, colloidal silica liquid (inorganic filler) (Nissan Chemical Co., Ltd. "Snowtex C"; solid content concentration 20)
%) And a 60% aqueous solution of SA-modified PVA in methanol [Kuraray Co., Ltd. "HM-N-O4" (number average molecular weight 22000, saponification degree 60 mol% and vinyl sulfonic acid ratio 0.4 mol%). Some SA-modified PVA 10
% Solution) dissolved in 100 parts of 60% aqueous methanol solution] 100 parts were stirred with a ball mill for a whole day and night to obtain a uniform emulsified dispersion. (2) In 100 parts of the dispersion obtained in (1) above, 0.8 part of glyoxal (crosslinking agent) and polyethyleneimine (amino compound) (manufactured by Nippon Shokubai Co., Ltd .: molecular weight 1000) 5
Part, Fluorine-based defoamer (M
EGAFAC, F-177 ") and 0.1 part of polyurethane resin (" TSP-202 "manufactured by Toyo Ink Mfg. Co., Ltd.
100 parts of a 30% dioxane solvent solution of "Medium") is added and stirred for 30 minutes, and the viscosity is 50 cps when measured with a Bruckner viscometer at a temperature of 25 ° C., so that the coating has a solid content concentration of 23.4%. A composition for use was obtained. In the obtained coating composition, the ratio of the polyurethane resin was 57.8 parts, the ratio of the SA-modified PVA was 15.4 parts, the ratio of the organic filler was 13.9 parts, and the inorganic filler per 100 parts of the total solid content. The ratio of 1.5 parts, the ratio of the cross-linking agent is 1.5 parts,
Amino compound ratio of 9.6 parts, antifoaming agent ratio of 0.2
It was a department.

(3) The coating composition obtained in (2) above was applied to a polyvinyl fluoride film (“EXCELAR # 20” manufactured by WH BRADY, using an applicator bar).
00 ") was coated so that the thickness of the coating layer after drying was 10 μm, and then dried at 130 ° C. for 5 minutes to obtain a polyvinyl fluoride film having the coating layer. When the adhesion and water resistance between the coating layer and the base film in the obtained coated film were examined by the methods described above, the results were as shown in Table 2 below. (4) Using the coated film obtained in (3) above, the ink adhesion, color developability, bleeding degree and oil absorption are tested by the methods described above, and the copy test by an electrostatic copying machine is performed by the method described above. As a result, the results were as shown in Table 2 below.

Example 2 A blocked polyisocyanate compound as a cross-linking agent instead of glyoxal "Elastron E-37" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .;
Heat-reactive water-soluble urethane resin; NCO active ingredient 25%)
And a chitosan as the amino compound in place of polyethyleneimine to prepare a coating composition in the same manner as in Example 1 except that the composition shown in Table 2 was used. The coating composition was prepared in the same manner as in Example 1. To coat a polyvinyl fluoride film and then dried at 130 ° C. for 5 minutes to produce a coated film. When the above-mentioned method for examining the adhesion and water resistance between the coating layer and the base film in the obtained coating film,
The results were as shown in Table 2 below. Further, using the above-obtained coated film, ink adhesion, color developability, bleeding degree, oil absorption and a copying test were conducted on an electrostatic copying machine by the above-mentioned method, as shown in Table 2 below. It was the result.

Example 3 A polyvinylidene fluoride film (KFC manufactured by Kureha Chemical Co., Ltd.) was used as a base film.
The same operations and tests as in Example 1 were carried out except that the film ") was used, and the results shown in Table 2 below were obtained.

Example 4 Urea as an organic filler
The same operations and tests as in Example 1 were performed except that 30 parts of a styrene-acrylic copolymer emulsion (“Grossdale” manufactured by Mitsui Toatsu Chemicals; resin solid content 30%) was used instead of the formalin-based resin. When I went, Table 2 below
The results shown in are obtained.

Example 5 The same operations and tests as in Example 1 were carried out except that a plasma-treated ethylene-tetrafluoroethylene copolymer film (manufactured by Daikin Chemical Co., Ltd.) was used as the base film. , Table 2 below
The results shown in are obtained.

Comparative Example 1 A coating composition was prepared in the same manner as in Example 1 except that the cross-linking agent glyoxal used in Example 1 was not used. The results shown in Table 3 below were obtained.

Comparative Example 2 A coating composition was prepared in the same manner as in Example 1 except that the SA-modified PVA was not used, and the same test was carried out.
The results shown in are obtained.

Comparative Example 3 A coating composition was prepared in the same manner as in Example 1 except that the organic filler urea-formalin resin used in Example 1 was not used, and the same test was conducted. As a result, the results shown in Table 3 below were obtained.

Comparative Example 1 Polypropylene synthetic paper having a porous structure [“Yupo VJF-90” manufactured by Nisshinbo Co., Ltd.) was used as a base film and was directly drawn on the synthetic paper by the method described above. The ink adhesion, color development, bleeding degree and oil absorption were examined, and a direct electrostatic copying machine was used to perform a copy test. The results are shown in Table 3 below.

[0062]

[Table 2]

[0063]

[Table 3]

From the results shown in Tables 2 and 3 above, it was confirmed that the polyurethane resin (A), the SA-modified PVA (B), the crosslinking agent (C), the organic filler (D) and the inorganic filler (E) were used. The coating compositions of the present invention of Examples 1 to 5 have a small surface free energy, a large affinity (adhesion) with a fluoropolymer having a very low affinity with most substances, and an excellent water resistance. In addition, the fluoropolymer film obtained by coating the coating composition of the present invention has affinity (adhesion) with ink or toner, color development, bleeding resistance, oil absorption (absorption rate). ) Is excellent and the colors are beautiful, and clear characters and images without bleeding can be printed or copied in a short time.

On the other hand, in the case of the coating composition of Comparative Example 1 containing no crosslinking agent (C), the adhesion between the coating layer and the base film and the water resistance of the coating layer were poor, In addition, the adhesion between the coating layer and the ink is low, and the oil absorption (ink absorption rate) is low, and it is difficult to form a coating film or a printing layer that is hard to peel off in a short time, and SA-modified PVA (B) is used. The coating composition of Comparative Example 2 containing no content and the coating composition of Comparative Example 3 containing no organic filler (D) have adhesion between the base film and the coating layer, water resistance of the coating layer, and a coating layer. In all of the ink adhesion, color development, bleeding resistance, oil absorption, and color development by a copying machine, Example 1 was used.
It can be seen that it is significantly inferior to ~ 5.

[0066]

The coating composition of the present invention has excellent properties such as adhesion to a substrate, water resistance and handleability, and a coating layer formed from the coating composition of the present invention has an aqueous property. ink,
With water-based paints, various toners, etc., it is possible to print, paint and copy beautifully and vivid color tones, letters, figures and images without bleeding efficiently in a short time with clear and good adhesion. The coating composition of the present invention is suitable as a surface coating material for films, sheets, and other products made of a fluoropolymer having a small surface free energy and an extremely low affinity with most substances. When a coating layer is formed on a substrate made of a fluoropolymer or other material using the coating composition of the present invention, an aqueous ink, an aqueous paint, an electrostatic copy which does not use an organic solvent are formed thereon. Since it is possible to directly form clear letters and images with beautiful color tone using toner for toner, the deterioration and destruction of the natural environment and work environment that has previously occurred by using organic solvents,
The danger of fire can be prevented. When the coating composition of the present invention is used, the above-mentioned printing, coating, electrostatic copying and the like can be directly carried out on the coating layer formed by the coating composition of the present invention, so that the steps are It does not go through multiple steps, has a small number of manufacturing steps, does not require manufacturing time, and is extremely advantageous in terms of cost.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08F 216: 14)

Claims (5)

[Claims] 1. A polyurethane resin (A), a sulfonic acid group-containing modified polyvinyl alcohol (B), a crosslinking agent (C), an organic filler (D) and an inorganic filler (E).
A coating composition comprising: 2. The weight ratio of organic filler (D): inorganic filler (E) is 99: 1 to 1:99, and {total weight of organic filler (D) and inorganic filler (E)}:
The weight ratio of the {total weight of the polyurethane resin (A) and the sulfonic acid group-containing modified polyvinyl alcohol (B)} is 10: 9.
The coating composition according to claim 1, which is 0 to 90:10. 3. The coating composition according to claim 1, further comprising an amino compound (F) and / or a surfactant (G). 4. The coating composition according to claim 1, which is for coating a fluoropolymer product. 5. An organic polymer product coated with the coating composition according to any one of claims 1 to 4.