WO2009151018A1 - 結晶性セルロース複合体を含む組成物 - Google Patents
結晶性セルロース複合体を含む組成物 Download PDFInfo
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- WO2009151018A1 WO2009151018A1 PCT/JP2009/060428 JP2009060428W WO2009151018A1 WO 2009151018 A1 WO2009151018 A1 WO 2009151018A1 JP 2009060428 W JP2009060428 W JP 2009060428W WO 2009151018 A1 WO2009151018 A1 WO 2009151018A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
- C09D101/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/18—Writing inks specially adapted for ball-point writing instruments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
Definitions
- the present invention relates to a composition having high stability, and when used as a paint, it does not easily cause sagging or peeling even when spray coating or baking, and has good interface control during wet-on-wet coating.
- Patent Document 1 describes a pigment dispersion paste for electrodeposition paint using a cellulose composite and an electrodeposition paint composition using the same.
- Patent Document 2 discloses that the standing stability of an inorganic pigment is improved using microcrystalline cellulose.
- Patent Document 3 discloses an aqueous resin paint that contains atomized cellulose and can be sprayed.
- Patent Document 4 discloses a technique in which crystalline cellulose is used in an ink composition for the purpose of preventing pigment settling.
- JP 2006-111699 A JP-A-5-132644 JP-A-5-163445 JP 2006-45248
- the dispersion stability of pigments can be imparted by using a cellulose composite by the conventional technology.
- it is used for electrodeposition coating, brush coating, and air-drying coating, and there is no report on coating by spray coating and baking.
- the coating method has a problem of preventing armpits and sagging. That is, in the case of electrodeposition coating, an object is immersed in an electrodeposition bath of a thin paint having a solid content of about 20% by mass, and an electrodeposition coating film is formed in advance by applying a voltage. And the technique of strengthening the electrodeposition coating film by baking is taken.
- multilayer coating is generally performed in applications that require long-term stability, such as automobiles.
- electrodeposition coating is first performed in order to make the metal barely rust.
- the electrodeposition coating has unevenness of the bare metal as it is, and is not smooth.
- overcoating two layers of a base coat and a top coat are usual is performed on the intermediate coating for the purpose of imparting design properties and weather resistance.
- a three-coat two-bake coating method is generally used in which intermediate coating is performed, baking is performed once to complete a coating film, and further, a base coat and top coat of a top coat are applied and further baking is performed.
- a method has been proposed in which an overcoating is performed without baking an intermediate coating layer, and the baking is performed at once. That is, it is said that the 3-coat 1-bake (3WET) coating method by wet-on-wet coating is more environmentally friendly.
- 3WET 3-coat 1-bake
- wet-on-wet coating when wet-on-wet coating is applied, new problems such as intermediate coating and top coating are mixed at the interface and the finished appearance is deteriorated and chipping resistance is deteriorated.
- water-based paints have been made more difficult because the latent heat of water is high and the paint takes time to dry.
- the present invention has high stability, and when used as a water-based paint, spray coating and baking do not easily cause sagging or peeling, and surprisingly, mixing at the interface when wet-on-wet coating is performed. It aims at providing the composition which can suppress this.
- the present inventors have obtained a composition having high pigment dispersion stability by using a cellulose composite composed of a specific hydrophilic polymer and crystalline cellulose.
- the composition contains a synthetic resin and a curing agent, and the solid content in the composition exceeds 25% by mass and the viscosity is 30 mPa ⁇ s or more, so that the storage stability of the paint is excellent, and the sag during spray coating and baking is excellent. It has been found that not only is it difficult to cause cracks, but also surprisingly, mixing at the interface when wet-on-wet coating is suppressed, and good appearance and chipping resistance can be exhibited.
- the present invention is as follows.
- a composition comprising 100 parts by mass of pigment, 0.01 to 50 parts by mass of a cellulose composite, and water, wherein the solid content of the composition exceeds 25% by mass and the viscosity is 30 mPa ⁇ S or more
- the cellulose composite has an acid value of 2.0 or more and a weight average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 7 of a hydrophilic polymer of 0.5 to 50% by mass and crystalline cellulose of 50 to 99.
- the composition as described above containing 5% by mass, and having an average particle size of 10 ⁇ m or less.
- the average particle size of the cellulose composite described in (1) is a solid content concentration of 1% dispersed in water for 20 minutes at 25 ° C. and 500 rpm using a propeller stirrer equipped with four paddle blades having a radius of 4 cm.
- the aqueous dispersion was 10 ⁇ m or less when measured as an aqueous dispersion and was dispersed under the same conditions as above except that the thixotropic index (TI value) of the cellulose composite was 2% solids concentration.
- the composition according to (1) which is 4 or more when measured as.
- the composition according to (5) comprising 50 to 3000 parts by weight of a dispersion aid with respect to 100 parts by weight of the cellulose composite.
- the composition according to (6) further comprising a synthetic resin and an additive.
- thixotropy index (TI value) of the cellulose composite was measured as an aqueous dispersion dispersed under the same conditions as described above except that the solid content concentration was 2%.
- An additive for a coating containing the cellulose composite which is 4 or more in some cases.
- High stability according to the present invention when used as a water-based paint, a composition with good interfacial control during wet-on-wet coating, in addition to a composition with good interface control during wet-on-wet coating.
- a composition with good interfacial control during wet-on-wet coating in addition to a composition with good interface control during wet-on-wet coating.
- the composition of the present invention comprises 0.5 to 50% by weight of a hydrophilic polymer having an acid value of 2.0 or more and a weight average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 7 , and crystalline cellulose 50 to 99.
- the composition contains 5% by mass of a cellulose composite having an average particle size of 10 ⁇ m or less, a pigment, and water, and the solid content of the composition exceeds 25% by mass and the viscosity is 30 mPa ⁇ s or more.
- the composition of the present invention further contains a synthetic resin and a curing agent, and is preferably used as a paint.
- the composition of the present invention can be suitably used for a cookie-type paint that forms a coating film by a baking process in which curing is accelerated by applying heat.
- the baking temperature of the coating is appropriately adjusted depending on the resin and additives used, but it is usually preferable to perform baking at 100 to 200 ° C. in order to obtain sufficient film properties. More preferably, it is 110 to 180 ° C, and most preferably 120 to 160 ° C.
- the baking time is appropriately adjusted according to the baking temperature, but 5 minutes or more is preferable in order to obtain sufficient film properties.
- the composition of the present invention can suppress the occurrence of sagging and flaming even when the heating time exceeds 5 minutes. It has a great effect.
- the composition of the present invention has a viscosity of 30 mPa ⁇ s or more. If the viscosity is less than 30 mPa ⁇ s, sagging is likely to occur during spray coating. Preferably it is 60 mPa * s or more, More preferably, it is 100 mPa * s or more. The upper limit is not particularly limited, but is usually 10 5 mPa ⁇ s or less.
- the viscosity here is the viscosity when measured at 60 rpm with a B-type viscometer using a suitable rotor with a paint.
- the hydrophilic polymer of the present invention preferably has an acid value of 2.0 or more and a weight average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 7 .
- the acid value of the hydrophilic polymer is more preferably 5 or more, and still more preferably 9 or more.
- the acid value is 100 or less, when the composition is used for coating, it is difficult for the resin component in the coating composition to aggregate.
- the acid value referred to here is expressed in mg of KOH required to neutralize the acid in 1 g of the hydrophilic polymer.
- the weight average molecular weight of the hydrophilic polymer of the present invention is preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 . If it is less than 1 ⁇ 10 3 , the two layers at the time of wet-on-wet coating tend to be mixed at the interface. Moreover, when it exceeds 1 ⁇ 10 7 , the surface smoothness of the coating film may be impaired. More preferably from 5 ⁇ 10 4 ⁇ 9 ⁇ 10 6.
- the molecular weight of the hydrophilic polymer can be determined by an ordinary method such as GFC.
- hydrophilic polymer examples include carboxymethylcellulose and salts thereof, xanthan gum, caraya gum, carrageenan, gum arabic, glucomannan, gellan gum, alginic acid and salts thereof, and ester bodies such as propylene glycol alginate.
- the crystalline cellulose of the present invention has an average degree of polymerization of 30 to 400 obtained by depolymerizing cellulose materials such as wood pulp and refined linter by acid hydrolysis, alkaline oxidative decomposition, enzymatic decomposition, etc. Means over 10%.
- the cellulose composite of the present invention comprises 0.5 to 50% by mass of a hydrophilic polymer and 50 to 99.5% by mass of crystalline cellulose.
- the cellulose composite of the present invention can be obtained, for example, by mixing crystalline cellulose and a hydrophilic polymer within the above ratio, wet grinding, drying and grinding.
- the cellulose composite of the present invention is dispersed in pure water with an Excel Auto homogenizer (ED-7 type, manufactured by Nippon Seiki Co., Ltd.) so that the concentration of the sample is 1% by mass, and is dispersed for 5 minutes at 15000 rpm.
- Excel Auto homogenizer ED-7 type, manufactured by Nippon Seiki Co., Ltd.
- the average particle size is 10 ⁇ m or less when the value at which the integrated volume is 50% is read by a scattering device (Horiba, Ltd., LA-910), and the average particle size is 10 ⁇ m or less. Those that do not cause obvious precipitation. For example, when each of the above components is simply powder-mixed, it cannot be sufficiently dispersed in water even by the above dispersion method, and precipitates are formed or the average particle size exceeds 10 ⁇ m. In such a case, it is not a cellulose composite but a simple mixture of crystalline cellulose and a hydrophilic polymer.
- the average particle size in the measurement method is 10 ⁇ m or less, but when considering the smoothness of the coating film when used as a paint The average particle size needs to be 10 ⁇ m or less.
- the smaller the average particle diameter the higher the effect of preventing sagging during spraying of the paint and the smoothness of the coating film tends to improve.
- the average particle diameter of the glass is not so small, that is, it is preferably 4 ⁇ m or more, more preferably 7 ⁇ m or more.
- the hydrophilic polymer When the hydrophilic polymer is less than 0.5% by mass, the dispersion stability of the composition tends to deteriorate. On the other hand, if it exceeds 50% by mass, there is a possibility that the paint is easily cracked. More preferably, it is 1 to 30% by mass, and most preferably 5 to 20% by mass.
- the cellulose composite of the present invention may contain components other than the hydrophilic polymer and crystalline cellulose.
- dextrins such as roasted dextrin, hydrolyzed starch, pullulan, xylose, glucose, fructose, sucrose, trehalose, cellooligosaccharide, xylooligosaccharide, fructooligosaccharide, galactooligosaccharide, raffinose and other sugars, xylitol, mannitol, erythritol, etc. It may contain 5 to 30% by mass of water-soluble molecules of sugar alcohols.
- the method of mixing components other than hydrophilic polymers and crystalline cellulose, such as dextrins does not need to be homogenized once with a high-pressure homogenizer or a high-speed stirrer as in the easily dispersible cellulose composite described later. You can mix them.
- the easily dispersible cellulose composite whose dispersibility is improved to a level dispersible with a propeller stirrer is further 50 to 3000 parts by weight, preferably 100 to 100 parts by weight of a dispersion aid with respect to 100 parts by weight of the crystalline cellulose composite. It may contain 2000 parts by mass, more preferably 200 to 1000 parts by mass.
- the cellulose composite When producing an easily dispersible cellulose composite, the cellulose composite may be produced in advance or may be produced by mixing each component of the cellulose composite and a dispersion aid. In mixing the components, all the components may be mixed at the same time or may be mixed one by one.
- the ratio of the hydrophilic polymer to the crystalline cellulose is as described above, but the cellulose composite used for the easily dispersible cellulose preferably has more water-soluble polymer. Specifically, a cellulose composite containing 5% by mass or more of a hydrophilic polymer is preferable.
- distribution adjuvant is 50 mass parts or more, sufficient dispersibility will be acquired, and if it is 3000 mass parts or less, in order to exhibit a function, a large addition amount is not required.
- the dispersion aid here is not particularly limited as long as it is easily soluble in water, for example, dextrins such as roasted dextrin and hydrolyzed starch, xylose, glucose, fructose, sucrose, trehalose, cellooligosaccharide, Sugars such as fructooligosaccharides, galactooligosaccharides, raffinose, sugar alcohols such as xylitol, mannitol, erythritol, aspartic acid, glutamic acid, lysine, arginine, histidine, glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, Examples include amino acids such as asparagine, glutamine, proline, phenylalanine, tyrosine, and tryptophan, and water-soluble salts such as citrate and sodium chloride.
- dextrins such
- water-soluble saccharides are preferable, and dextrin having DE (starch saccharification) of 5 to 40 is particularly preferable from the viewpoint of safety and productivity.
- DE starch saccharification
- One or a mixture of these can be used as a dispersion aid.
- mixing of each component cannot achieve easy dispersion only by mixing with powder.
- a production method is preferred in which is dried with a spray dryer or the like.
- a commercially available crystalline cellulose composite for example, Theolas RC-N30 (trade name) (manufactured by Asahi Kasei Chemicals Co., Ltd.)
- a dispersion aid by the above method to easily disperse cellulose composite. It is good.
- the high-pressure homogenizer here is a device that pressurizes a raw material (liquid or liquid and solid) and performs pulverization / dispersion / emulsification using shearing force when passing through a gap (slit).
- a raw material liquid or liquid and solid
- microfluidizer trade name
- Alite trade name
- APV homogenizer trade name
- the easily dispersible cellulose composite of the present application is a cellulose composite as defined above, and has an average particle size of 10 ⁇ m or less and a thixotropy index (TI value) of 4 or more by the following dispersion method.
- the average particle size is such that a cellulose composite and deionized water can be sufficiently stirred in a general 1-2 L stainless beaker so that a dispersion of 1% by mass in terms of cellulose can be obtained, for example, 700 ml in a 1 L beaker. It is defined as the average particle size when charged and dispersed in water for 20 minutes at 25 ° C.
- the lower limit is not particularly limited, but 1 ⁇ m or more is preferable for the weak dispersion as described above.
- the radius of the paddle blade used here may be slightly different from 4 cm. For example, a four-blade angled fan with a blade diameter of 80 mm from the Magella (trade name) NZ-1000 series and a general-purpose agitator blade cross with a three-one motor (radius 35 mm) can be mentioned.
- the thixotropy index (TI value) as used in the present invention is the same method as described above except that the dispersion concentration is 2% by mass in terms of cellulose, that is, the cellulose composite and deionized water are placed in a 1-2 L container. Using a propeller stirrer equipped with a 4 cm paddle blade with a radius of 4 cm, the dispersion dispersed in water at 25 ° C. and 500 rpm for 20 minutes was mixed with a B-type viscometer, rotor No.
- TI value viscosity of 6 rpm / viscosity of 60 rpm.
- the higher the TI value the stronger the structural viscosity, the less sagging, and the better the storage stability.
- the TI value of the dispersion obtained by the aforementioned operation of the easily dispersible cellulose composite of the present invention is preferably 4 or more. More preferably, it is 5 or more, and most preferably 6 or more. When the TI value is 4 or more, the storage stability does not deteriorate.
- the upper limit is not particularly limited, but the TI value of a normal cellulose composite is 20 or less.
- a normal cellulose composite or a readily dispersible cellulose composite can be used, but when a dispersion facility is prepared, it is more cost-effective to use a normal cellulose composite. .
- an easily dispersible cellulose composite should be used.
- (easily dispersible) cellulose composite refers to both a normal cellulose composite and an easily dispersible cellulose composite.
- the absolute value of the zeta potential of the (easily dispersible) cellulose composite of the present invention is preferably 30 mV or more.
- the zeta potential here refers to a crystalline cellulose complex in pure water in a 0.5% dispersion in terms of cellulose, and the zeta potential of the dispersion is adjusted to pH 2-12 using a zeta potential meter (ELSZ, manufactured by Otsuka Electronics Co., Ltd.). This is the value of the point with the largest absolute value. Usually, it becomes maximum in the range of pH 5-8.
- the absolute value of the zeta potential of the cellulose composite is preferably 30 mV or more, more preferably 50 mV or more, and still more preferably 60 mV or more.
- the (easily dispersible) cellulose composite of the present invention usually exhibits a negative charge. If the absolute value of the zeta potential is 30 mV or more, the effect of the present invention is sufficiently obtained.
- the pigment used in the present invention is not particularly limited, and the shape of the pigment is not particularly limited, such as a plate shape, a spherical shape, or a scale shape, and can be used.
- the shape of the pigment is not particularly limited, such as a plate shape, a spherical shape, or a scale shape, and can be used.
- Anticorrosive pigments such as bismuth silicate, hydrotalcite, zinc dust, mica-like iron oxide, calcium carbonate, barium sulfate, alumina white, silica, diatomaceous earth, kaolin, talc, clay, mica, barita, organic bentonite, white carbon Body pigments such as titanium
- the primary average particle diameter of the pigment is preferably 10 ⁇ m or less. More preferably, it is 5 ⁇ m or less. If it is 10 micrometers or less, there is no possibility that dispersion stability will fall or the smoothness of a coating film will be impaired. Although there is no restriction
- Particularly preferred pigments for the paint of the present application include carbon black, titanium white, titanium dioxide, talc, clay, kaolin and the like.
- composition of the present invention When used for a water-based paint, it may be prepared by mixing all raw materials at the same time. However, a pigment dispersion paste is prepared by previously mixing a pigment and an (easily dispersible) cellulose composite. Is preferred.
- the mixing of the pigment and the cellulose composite is preferably performed in the presence of water by a disperser that requires grinding power, such as an SG mill, a ball mill, or an attritor. It is preferable to use a disperser having such a grinding power as described above, since the function can be efficiently imparted while releasing the secondary aggregation of the pigment.
- the mixing ratio of the pigment and the cellulose composite is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the pigment. When a disperser with high grinding power cannot be used, an easily dispersible cellulose composite is used. The amount of the easily dispersible cellulose composite added to the pigment is the same as that of a normal cellulose composite in terms of the cellulose composite.
- the required amount of the easily dispersible cellulose composite increases by the amount of the dispersion aid.
- the stability of pigment dispersion is not sufficiently imparted, the storage stability of the paint using the composition is deteriorated, and sagging and sag suppression during spraying are suppressed. It is difficult to obtain an effect and a wet-on-wet interface control function. Even if it exceeds 50 parts by mass, the effect of the present invention tends not to be improved, which may cause waste. More preferred is 0.1 to 40 parts by mass, and further more preferred is 0.3 to 30 parts by mass.
- water is contained at 10% by mass or more and less than 75% by mass with respect to the total solid content at the time of mixing. More preferably, it is 20 to 60% by mass.
- water is mixed at 10% by mass or more, secondary aggregation of the pigment can be sufficiently solved, and there is no possibility of causing unevenness in the coating film.
- productivity falls that it is 75 mass% or more, it is unpreferable.
- one or more additives such as a pigment dispersant, a surfactant, a curing agent, an antifoaming agent, an organic solvent, a thixotropic agent, a resin, and a glittering material are included as necessary. It doesn't matter.
- a dispersant such as a surfactant in combination.
- the pigment content is preferably 0.5 to 50% by mass, more preferably 1 to 45% by mass, and still more preferably based on the total amount of the paint.
- a composition in which a pigment is dispersed so as to be 2 to 40% by mass, a synthetic resin, a curing agent, and, if necessary, water and other additives are mixed. If the pigment content is 0.5% by mass or more, sufficient storage stability, smoothness of the coating film, and hiding power can be obtained. If it is 50 mass% or less, the amount of resin and water will not be relatively reduced, and the film formability and fluidity will not deteriorate.
- Examples of the synthetic resin used in the paint of the present invention include a water-based acrylic resin, a modified acrylic resin, a water-based urethane resin, a water-based acrylic urethane resin, a water-based vinyl chloride resin, a water-based vinyl acetate resin, a water-based epoxy resin, a water-based polyester resin, and a water-based alkyd. Resin and aqueous polyamide resin can be used.
- a synthetic polymer emulsion can be used as the synthetic resin.
- synthetic polymer emulsions include styrene-butadiene copolymer latex, polystyrene polymer latex, polybutadiene polymer latex, acrylonitrile-butadiene copolymer latex, polyurethane polymer latex, polymethyl methacrylate heavy polymer.
- the synthetic resin of the present invention is preferably an anionic synthetic resin.
- anionic synthetic resins it is preferable to use an aqueous polyester resin or an aqueous alkyd resin. Of course, these resins may be modified.
- curing agent used in the present invention examples include amino resins (melamine resins) and block polyisocyanate compounds. Of course, these resins may be modified.
- At least one of these curing agents is used.
- a polyester resin is used as a synthetic resin and a melamine resin is used as a curing agent.
- Examples of the monomer constituting the resin include aliphatic conjugated dienes such as butadiene, isoprene, 2-chloro-1, and 3-butadiene, aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene, Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, alkyl acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, vinyl cyanides such as acrylonitrile and methacrylonitrile Examples of the compound include vinyl acetate, vinyl chloride, vinylidene chloride, urethane, and ethylene.
- ethylenically unsaturated carboxylic acids such as itaconic acid, fumaric acid, acrylic acid, methacrylic acid and crotonic acid.
- the amount of (total) synthetic resin in the paint is preferably 80 to 500 parts by weight, more preferably 150 to 450 parts by weight, most preferably 200 to 100 parts by weight of the (total) solid content of the pigment in the paint. 400 parts by weight is desirable. If the mass ratio of the synthetic resin is 80 parts by mass or more, there is no possibility of adversely affecting fluidity and film formability. Moreover, if it is 500 mass parts or less, a color nonuniformity etc. will not arise.
- composition of the present invention may further contain an additive as necessary.
- additives include amino group-containing epoxy resins such as tertiary amine type, quaternary ammonium salt type epoxy resins, quaternary ammonium salt type resins, pigment dispersants such as surfactants, polydimethylsiloxane, modified silicone compounds, Antifoaming agents such as fatty acid esters, polyacrylic acid polymers, polyamides, organic clays, thickeners such as hydroxyethylcellulose, carboxymethylcellulose, dibutyltin laurate, dibutyltin oxide, dibutyltin oxide, dioctyltin oxide, dibutyltin dibenzoate, etc.
- anti-scratching / non-adhesive agents examples thereof include anti-scratching / non-adhesive agents, anti-coloring agents such as silicone oil, surfactants, wetting agents such as alkyl phosphates and polyamides, and organic solvents such as alcohols. If necessary, an appropriate amount is used depending on the intended use / function of an additive comprising one or a combination of two or more selected from these.
- organic solvent examples include one or more selected from hydrocarbons, alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, and carbonates.
- the solvent which consists of a combination is mentioned.
- hydrocarbons examples include xylene, toluene, hexane, cyclohexane, mineral spirit, turpentine oil, sorben naphtha, and the like.
- alcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, n-undecanol, and these Isomers, cyclopentanol, cyclohexanol and the like.
- Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexane Examples include diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like.
- Polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Examples include ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and cellosolve acetate.
- ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
- Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactic acid ester, butyric acid ester, dibutyl phthalate, dioctyl phthalate, and cyclic such as ⁇ -caprolactone and ⁇ -caprolactam Examples include esters.
- ethers include diethyl ether, isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.
- carbonates examples include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and ethylene carbonate.
- the composition of the present invention is suitably used as a paint for spray coating, and the solid content exceeds 25% by mass. More preferably, it is 30 mass% or more, More preferably, it is 35 mass% or more. When the solid content is 25% by mass or less, sagging after spraying is likely to occur, and since there are many volatile components, drying takes time.
- the upper limit is preferably less than 85% by mass from the viewpoint of spray workability.
- the coating of the present invention can be performed by various methods, but spray coating is particularly preferable from the viewpoint of clarifying the effect of the present invention.
- spray coating is particularly preferable from the viewpoint of clarifying the effect of the present invention.
- spray coating is particularly preferable from the viewpoint of clarifying the effect of the present invention.
- spray device to be used is not particularly limited, and examples thereof include a low pressure spray gun, an automatic spray gun, an air brush, a long neck spray gun, a turbulent yarn spray gun, a bell type coating machine, and a disk type coating machine.
- shower coating often has a problem of sagging, and is synonymous in the present invention.
- the base material to be painted is selected according to its use such as construction, building materials, structures, ships, fishnets, automobiles, electronic parts, metals, plastics, machinery, railways, aircraft, woodworking, home use, road surface display, leather use, etc.
- the composition of the present invention is preferably used as an aqueous paint for construction and building materials, an aqueous paint for automobiles, an aqueous paint for marine steel plates, an aqueous paint for cans, a paint for PCM, and an organic surface treatment paint.
- it can be suitably used for an aqueous intermediate coating for automobiles.
- the composition of the present invention is particularly suitable for the process of wet-on-wet coating and baking.
- Wet-on-wet coating refers to a method in which the upper layer is coated in a wet state by omitting the lower layer baking step when two or more layers are coated. Since the baking process can be reduced, there is an effect of reducing the environmental load and energy, but it is necessary to improve the interface control force with respect to the wet interface.
- the number of layers to be applied by wet-on-wet is not particularly limited, but a 3-coat 1-bake coating process is generally used, and is preferably used in this process.
- the composition comprises a pigment dispersion composition using an easily dispersible cellulose composite, a film-forming resin, and an additive.
- the pigment used in the ink is not particularly limited, and any of inorganic and organic pigments can be used, and inorganic fluorescent pigments and organic fluorescent pigments can also be used.
- inorganic pigments include carbon black, titanium oxide, bengara, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, yellow lead, and molybdate orange.
- organic pigments include azo lakes, insoluble azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dye lakes, nitro pigments, and nitroso pigments.
- phthalocyanine blue C.I. 74160
- phthalocyanine green C.I. 74260
- Hansa Yellow 3G C.I. 11670
- disazo yellow GR C.I. 21100
- permanent red 4R C.I. 12335
- brilliant carmine 6B C.I. 15850
- quinacridone red C.I. 46500
- an inorganic fluorescent pigment for example, a heavy metal salt such as zinc sulfide or a sulfide of alkaline earth metal is used as a raw material, and a trace amount of an activator such as copper, silver, or manganese is added to these high-purity ones.
- the organic fluorescent pigment examples include a solid resin obtained by dissolving a fluorescent dye in a synthetic resin vehicle, or a dispersion of resin fine particles obtained by emulsion polymerization, suspension polymerization, or the like, and a synthetic resin.
- vinyl chloride resin alkyd resin, alkali resin, etc. I. Acid Yellow 7, C.I. I. Basic Red 1 etc. can be used.
- These pigments can be used alone or in combination of at least two kinds.
- the average particle size of the pigment is preferably 10 ⁇ m or less. More preferably, it is 5 micrometers or less, Most preferably, it is 3 micrometers or less.
- the (total) content of the pigment is preferably in the range of 0.5 to 30% by mass, more preferably 2 to 30% by mass, and still more preferably 5 to 15% by mass with respect to the total amount of the ink.
- a resin, an additive, and water it is desirable to prepare the pigment dispersion composition of the present invention, a resin, an additive, and water as necessary. If it is 0.5% by mass or more, there is no possibility that the print density is insufficient, and if it is 30% by mass or less, the writing comfort does not tend to be remarkably heavy.
- a pigment, an easily dispersible cellulose composite, a resin, an additive, and water may be mixed to obtain a pigment dispersion composition without preparing a pigment dispersion composition in advance, and the ink of the present invention may be used.
- Examples of the film-forming resin used in the ink of the present invention include styrene butadiene resin, acrylonitrile butadiene resin, carboxy-modified styrene butadiene copolymer resin, acrylic resin, rosin-modified phenol resin, and rosin-modified alkyd resin.
- the film-forming resin used in the ink of the present invention it is preferable to use a resin emulsion from the viewpoint of easy adjustment of ink viscosity and the like.
- the resin emulsion include a styrene butadiene resin emulsion, an acrylonitrile butadiene resin emulsion, a carboxy-modified styrene butadiene copolymer resin emulsion, and an acrylic resin emulsion.
- a styrene butadiene resin emulsion an acrylonitrile butadiene resin emulsion
- a carboxy-modified styrene butadiene copolymer resin emulsion emulsion
- acrylic resin emulsion emulsion.
- One kind or a mixture of two or more kinds of these resins can be used.
- the total content of these resins is preferably 10 to 50% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass with respect to the total amount of ink.
- the content of the film-forming resin is 10% by mass or more, the film-forming property is not inferior and there is no case where clear printing is not achieved.
- it is 50 mass% or less, there is no tendency for the stability of ink to deteriorate.
- additives used in the ink of the present invention for example, wettability improvers such as lecithin, sorbitan fatty acid ester, alkylamine fatty acid salt, fluidity modifiers such as higher alcohols, organic solvents, surfactants, gelling agents, Examples include antibacterial agents, antioxidants, ultraviolet absorbers, thickeners, and organic solvents.
- wettability improvers such as lecithin, sorbitan fatty acid ester, alkylamine fatty acid salt
- fluidity modifiers such as higher alcohols, organic solvents, surfactants, gelling agents.
- antibacterial agents antioxidants, ultraviolet absorbers, thickeners, and organic solvents.
- organic solvent examples include one or more selected from hydrocarbons, alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, and carbonates.
- the solvent which consists of a combination is mentioned.
- polyhydric alcohols are preferable from the viewpoint of safety and function.
- Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexane Examples include diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like.
- hydrocarbons examples include xylene, toluene, hexane, cyclohexane, mineral spirit, turpentine oil, sorben naphtha, and the like.
- alcohols examples include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, n-undecanol, and these Isomers, cyclopentanol, cyclohexanol and the like.
- Polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Examples include ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and cellosolve acetate.
- ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
- Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactic acid ester, butyric acid ester, dibutyl phthalate, dioctyl phthalate, and cyclic such as ⁇ -caprolactone and ⁇ -caprolactam Examples include esters.
- ethers include diethyl ether, isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.
- carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and ethylene carbonate.
- the ink of the present invention has excellent storage stability, and is useful as a writing instrument such as a fountain pen, a ballpoint pen, a sign pen, and an ink for inkjet.
- ⁇ Average particle size of cellulose composite> (1) The sample was dispersed at 15000 rpm for 5 minutes with an Excel auto homogenizer (manufactured by Nippon Seiki Co., Ltd., ED-7 type) so that the concentration of the sample was 1% by mass. (2) Using a laser diffraction scattering apparatus (LA-910, manufactured by Horiba, Ltd.), the value at which the integrated volume was 50% was read and used as the average particle diameter.
- ⁇ Measurement of acid value> A 1 g sample (in terms of solid content) was accurately weighed and dissolved by adding about 200 ml of water.
- ⁇ Ink evaluation method> [Evaluation method of stability over time] Each of the obtained inks was stored in a transparent container (30 ml) with a lid, stored in a thermostatic bath at 50 ° C. and left for 2 weeks, and then the container was gently taken out, and the temporal stability was evaluated according to the following evaluation criteria. Evaluation criteria: ⁇ (excellent): No sedimentation separation is observed, and no change is seen from the initial stage. ⁇ (good): Sedimentation separation is observed slightly, but almost no change is seen from the initial stage. ⁇ (possible): Although the supernatant is confirmed by sedimentation separation, the sedimentation is bulky.
- a dispersion was prepared in the same manner as when the TI value was determined at a sample concentration of 1% by mass.
- a value (median diameter) at which the integrated volume was 50% was read by a laser diffraction scattering apparatus (LA-910, manufactured by Horiba, Ltd.) and used as an average particle diameter.
- Example 1 and Comparative Examples 1 and 2 Add 20.5 parts by mass of ethylene glycol, 12.9 parts by mass of trimethylolpropane, 51.7 parts by mass of phthalic anhydride, conduct an esterification reaction at 180 ° C. for 5 hours, and further add 14.9 parts by mass of trimellitic anhydride. In addition, it was reacted at 180 ° C. for 1 hour to obtain a polyester resin.
- DP pulp was cut with a shredder and hydrolyzed at 105 ° C. for 60 minutes under 1% by mass hydrochloric acid. The obtained acid-insoluble residue was filtered and washed with pure water to obtain a wet cake of crystalline cellulose.
- the water-soluble polymer Karaya gum having an acid value of 28.6 and a weight average molecular weight of 9 ⁇ 10 6 and dextrin with respect to the solid content of the wet cake and a ratio of crystalline cellulose / karaya gum / dextrin of 80/10 / 10 (solid mass ratio), kneading and grinding with a kneader, drying and pulverization to obtain a cellulose composite A.
- TPA block isocyanate resin
- -B80E solid content 80% by mass, manufactured by Asahi Kasei Chemicals Corporation was added to obtain an aqueous baking coating composition A (total solid content 49%).
- aqueous baking coating composition A is spray-coated on a commercially available test steel plate so that the dry film thickness is about 30 ⁇ m, and the aqueous base paint A is similarly applied so that the dry film thickness is about 15 ⁇ m by wet-on-wet, The film was set for about 10 minutes, preheated at 100 ° C. for 10 minutes, and then baked at 160 ° C. for 30 minutes to obtain a coating film.
- Example 1 As a comparison, after the aqueous baking coating composition A was baked under the same conditions, the aqueous base coating A was applied and baked. Thereafter, the aqueous baking coating composition A and its coating film were evaluated.
- the evaluation results are shown in Table 1.
- Comparative Example 1 the same procedure as in Example 1 was performed except that the Karaya gum was replaced with crystalline cellulose when the cellulose composite A was prepared.
- Comparative Example 2 the coating material of Example 1 was diluted with pure water so that the solid content was 20% by mass and evaluated in the same manner.
- Example 2 and Comparative Examples 3 and 4 Commercially available DP pulp was cut and hydrolyzed at 121 ° C. for 60 minutes under 0.6 mass% hydrochloric acid.
- the obtained acid-insoluble residue was filtered and washed with pure water to obtain a wet cake of crystalline cellulose.
- the ratio of crystalline cellulose / xanthan gum / dextrin is 75/5 with respect to the solid content of the wet cake, water-soluble polymer xanthan gum having an acid value of 9.5 and a number average molecular weight of 2 ⁇ 10 6. / 20 (solid content mass ratio), kneading and grinding with a kneader, drying and pulverization to obtain a cellulose composite B.
- composition B was obtained.
- 212 manufactured by Mitsui Cytec Co., Ltd.
- the aqueous baking coating composition B is air spray-coated on a commercially available test plate coated with an electrodeposition coating film so that the dry film thickness is about 20 ⁇ m, and the aqueous base paint A is 15 ⁇ m in dry film thickness by wet-on-wet.
- Comparative Example 3 the solid content of the coating material was diluted with pure water so that the solid content would be 23% by mass, and evaluated in the same manner.
- Example 3 and Comparative Example 5 Commercially available DP pulp was cut and hydrolyzed at 115 ° C. for 60 minutes under 0.5 mass% hydrochloric acid. The obtained acid-insoluble residue was filtered and washed with pure water to obtain a wet cake of crystalline cellulose.
- a water-soluble polymer carboxymethylcellulose sodium having an acid value of 2 and a weight average molecular weight of 5 ⁇ 10 4 is used, and the ratio of crystalline cellulose / carboxymethylcellulose sodium is 89/11 (solid content Mass ratio), kneading and grinding with a kneader, drying and pulverization to obtain a cellulose composite C.
- a cellulose composite C 0.5 parts by mass of this cellulose composite C, 40 parts by mass of red iron oxide, and 59 parts of deionized water were mixed and dispersed and mixed with an SG mill to obtain a pigment dispersion composition C (solid content: 41% by mass).
- the aqueous baked paint composition C is spray-coated on a commercially available test plate on which an electrodeposition coating is applied so that the dry film thickness is about 40 ⁇ m, and the aqueous base paint A is about 10 ⁇ m in wet-on-wet form.
- the film was pre-heated at 60 ° C. for 10 minutes, and then baked and dried at 150 ° C. for 20 minutes to obtain a coating film.
- the aqueous baking coating composition C was baked under the same conditions, the aqueous base coating A was applied and baked.
- the aqueous baking coating composition C and its coating film were evaluated. The evaluation results are shown in Table 1.
- Comparative Example 5 the same procedure was performed except that the crystalline cellulose was replaced with sodium carboxymethylcellulose.
- Example 4 and Comparative Example 6 Commercially available DP pulp was cut and hydrolyzed at 126 ° C. for 60 minutes under 0.65 mass% hydrochloric acid. The obtained acid-insoluble residue was filtered and washed with pure water to obtain a wet cake of crystalline cellulose.
- a water-soluble polymer carboxymethylcellulose sodium having an acid value of 2 and a weight average molecular weight of 5 ⁇ 10 4 and an acid value of 9.5 and a number average molecular weight of 2 ⁇ 10 6 with respect to the solid content of the wet cake.
- Water-soluble polymer xanthan gum and dextrin and edible oil (rapeseed oil)
- the ratio of crystalline cellulose / sodium carboxymethylcellulose / xanthan gum / dextrin / edible oil (rapeseed oil) is 73/5 / 2.8 / 19 / 0.2
- the mixture was kneaded and ground with a kneader, dried and pulverized to obtain a cellulose composite D.
- 21.6 mass parts of water-based alkyd resin (Aquable 48E, solid content 50 mass%, Showa Varnish Co., Ltd. product)
- 60.0 mass parts of titanium dioxide, 9.9 mass parts of deionized water, dimethylethanolamine 0.8. 1 part by mass and 0.3 parts by mass of the cellulose composite D were dispersed for 1 hour by a ball mill to obtain a pigment dispersion composition D (solid content: 85% by mass).
- the aqueous baked paint composition D is spray-coated on a commercially available test plate coated with an electrodeposition coating film so that the dry film thickness is about 20 ⁇ m, and the aqueous base paint A is about 15 ⁇ m wet-on-wet.
- the film was coated, preheated at 80 ° C. for 10 minutes, and then baked and dried at 140 ° C. for 20 minutes to obtain a coating film.
- the aqueous baking coating composition D was baked under the same conditions, the aqueous base coating A was applied and baked.
- the aqueous baking coating composition D and its coating film were evaluated. The evaluation results are shown in Table 1.
- Comparative Example 6 a powder obtained by mixing each component without kneading and grinding with a kneader was used. That is, a wet cake of crystalline cellulose was pulverized by drying and pulverizing, and the powder of each component and edible fat were put in a plastic bag at the above mixing ratio and well shaken and mixed.
- Trehalose was added to the dispersion so that the ratio of cellulose / trehalose was 60/40 (solid content mass ratio), and the mixture was further stirred for 20 minutes.
- the dispersion solution was ground by one pass at a pressure of 15 MPa using a high-pressure homogenizer (manufactured by APV), and then the inlet temperature was 90-100 ° C. and the outlet temperature was 70-80 ° C. using a spray dryer. It spray-dried on conditions, and the easily dispersible cellulose composite alpha was obtained.
- the average particle diameter of the dispersion liquid of the easily dispersible cellulose composite ⁇ was 7 ⁇ m, and the TI value was 4.2.
- This dispersion / dissolved solution was ground by one pass at a pressure of 20 MPa using a high-pressure homogenizer (manufactured by APV), and then the inlet temperature was 90-100 ° C. and the outlet temperature was 70-80 ° C. using a spray dryer. It spray-dried on conditions, and obtained the easily dispersible cellulose composite (beta).
- the average particle size of the dispersion of the easily dispersible cellulose composite ⁇ was 9 ⁇ m, and the TI value was 6.0.
- Sodium carboxymethylcellulose was added so that the cellulose / carboxymethylcellulose sodium ratio was 89/11 (solid content mass ratio) with respect to the solid content of the wet cake, and kneading and grinding were performed with a kneader.
- the obtained cellulose composite wet cake was added to hot water at 80 ° C. so as to have a solid concentration of 15% by mass and dispersed.
- Dextrin was added to the dispersion so that the cellulose / dextrin ratio was 60/40 (solid content mass ratio), and the mixture was further stirred for 20 minutes.
- the dispersion solution was ground by one pass at a pressure of 15 MPa using a high-pressure homogenizer (manufactured by APV), and then the inlet temperature was 90-100 ° C. and the outlet temperature was 70-80 ° C. using a spray dryer. Spray-drying was performed under conditions to obtain an easily dispersible cellulose composite ⁇ .
- the average particle size of the dispersion of the easily dispersible cellulose composite ⁇ was 6 ⁇ m, and the TI value was 8.5.
- ⁇ Preparation of pigment dispersion composition> (Examples 5 to 8 and Comparative Examples 7 to 10) Easily dispersible cellulose composites obtained in Production Examples 1 to 4 and cellulose composite ⁇ (Theorus RC-591 (trade name), manufactured by Asahi Kasei Chemicals Corporation, average particle diameter of 21 ⁇ m under the measurement conditions of the present invention, TI Value 2.9), cellulose composite ⁇ (Theorus RC-N81 (trade name), manufactured by Asahi Kasei Chemicals Corporation, average particle size 38 ⁇ m, TI value 1.8 under the measurement conditions of the present invention), and cellulose composite ⁇
- a pigment dispersion composition was prepared using the cellulose composite easy dispersion stabilizer disclosed in Example 1 of JP-A-2006-296302 (Document 8), average particle diameter of 11 ⁇ m, TI value of 3.9.
- Comparative Example 8 the cellulose composite ⁇ was preliminarily dispersed for 5 minutes at 15,000 rpm in advance with an Excel Auto Homogenizer (manufactured by Nippon Seiki Co., Ltd., ED-7 type), and the dispersion was used to remove pigments and the like using a high-speed impeller stirrer ( H4 was obtained by dispersing with a high-speed disperser.
- Table 3 shows the evaluation of these pigment dispersion compositions.
- the pigment dispersion compositions J1 to J4 were good in both storage stability and redispersibility.
- H1 to H3 precipitation and separation of the pigment occurred.
- H3 has easy dispersibility that can give sufficient sedimentation stability in the food field, so its storage stability and redispersibility were better than H1 and H2, but it never completely returned to the state prior to storage. There wasn't.
- H1, H2, and H3 use cellulose composites, their functions could not be sufficiently exhibited because the dispersing device cannot be sufficiently dispersed with a high-speed impeller-stirrer.
- Example 9 Using the pigment dispersion composition J4 obtained in Example 8, an aqueous coating composition was prepared and evaluated with the following composition. The evaluation of the coating film was performed on the coating film obtained by applying it to a test plate of calcium oxalate plate with an applicator and drying it in an oven at 110 ° C. for 1 hour. Each component was mixed by stirring with a high-speed impeller stirrer at 1000 rpm for 30 minutes. In Comparative Example 11, the same water-based paint was prepared and evaluated except that the pigment dispersion composition J4 was replaced with the pigment dispersion composition H1. The results are shown in Table 4.
- J4 or H1 pigment dispersion composition
- Acrylic resin emulsion synthetic resin; solid content 40%
- E410 Asahi Kasei Chemicals
- B. P plasticizer 2 parts by weight
- Texanol film-forming aid
- Comparative Example 11 was not only poor in storage stability and redispersibility, but also deteriorated in coatability and the like, as in the pigment dispersion composition used.
- Example 10 and Comparative Example 12 A water-based paint was prepared with the following composition. The components were mixed with a high-speed impeller stirrer at 1000 rpm for 30 minutes.
- Comparative Example 12 the easily dispersible cellulose composite ⁇ of Example 10 was converted into a cellulose composite ⁇ (Theorus RCN-81 (trade name), manufactured by Asahi Kasei Chemicals Corporation, average particle diameter of 38 ⁇ m under the measurement conditions of the present invention, The same procedure was performed replacing the TI value of 1.8). Evaluation of the coating film was performed using the obtained coating composition applied to a commercially available test plate and treated at 140 ° C. for 20 minutes. The evaluation results are shown in Table 5.
- Polyester resin emulsion solid content 30% by mass
- 13 parts by mass of pigment dispersion paste [SF611 White (manufactured by Toyo Ink), solid content 73%]
- Curing agent solid content 80% by mass
- 15 parts by mass [Polyamine-based curing agent (Ancamide 502)] 1 part by mass of easily dispersible cellulose composite ⁇
- Comparative Example 12 was not only poor in storage stability and re-dispersibility, but also generated fuzz as in the pigment dispersion paste used. (Example 11) The following ingredients were produced by the following method to obtain an ink.
- Pigment 8% by mass of aqueous dispersion of pink resin particles [SW-17 (Shinloihi), solid content 42%]
- Film-forming resin 60% by mass of aqueous dispersion of acrylonitrile-butadiene copolymer [Nipol LX517A (manufactured by Nippon Zeon), solid content 40%] 18% by weight of urea Dispersion stabilizer: Easily dispersible cellulose composite ⁇ 2% by mass 14% by mass of water (purified water)
- the above ingredients were sequentially added to the tank with stirring, and mixed and stirred with a high-speed impeller-stirrer 1500 rpm until uniform, and then filtered through a 1 ⁇ m bag filter to produce an ink.
- Example 12 The following ingredients were produced by the following method to obtain an ink.
- Pigment Orange resin particle aqueous dispersion 4% by mass [SW-14 (Shinloihi, solid content 42%)] Film-forming resin: 60% by mass of an aqueous dispersion of styrene-butadiene copolymer resin [Nipol LX438C (manufactured by Nippon Zeon), solid content 45%] Dispersion stabilizer: Easily dispersible cellulose composite ⁇ 1% by mass 15% by weight of urea 20% by mass of water (purified water) The above ingredients were sequentially added to the tank with stirring, mixed and stirred with a high-speed impeller-stirrer 1500 rpm until uniform, and then filtered through a 1 ⁇ m bag filter to produce an ink.
- Comparative Example 13 The easily dispersible cellulose composite ⁇ of Example 12 was changed to a cellulose composite ⁇ Theolas RC-591 (trade name), manufactured by Asahi Kasei Chemicals Corporation, an average particle diameter of 21 ⁇ m under the measurement conditions of the present invention, and a TI value of 2.9). Instead, others made ink with the same recipe. In Comparative Example 13, a large amount of residue was generated in the bag filter. The ink obtained as described above was evaluated by the method described above. The results are shown in Table 6.
- Examples 11 and 12 were superior to Comparative Example 13 in both aging stability and viscosity aging stability. This is because in Comparative Example 13, the cellulose composite cannot be sufficiently dispersed and remains in the bag filter, so that the function cannot be expressed.
- composition of the present invention has good storage stability, and when used as a paint, it can be spray-painted, has little sagging and wrinkles, and is suitable for wet-on-wet paint. It can be suitably used.
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Abstract
Description
(1)顔料100質量部、セルロース複合体0.01~50質量部、及び水を含む組成物であって、該組成物の固形分が25質量%を超えて、かつ粘度が30mPa・S以上であり、並びに該セルロース複合体は、酸価2.0以上で且つ重量平均分子量が1×103~1×107の親水性高分子0.5~50質量%及び結晶性セルロース50~99.5質量%を含み、該セルロース複合体の平均粒径が10μm以下である、上記組成物。
(2)さらに合成樹脂及び硬化剤を含む、(1)に記載の組成物。
(3)前記合成樹脂がアニオン型合成樹脂である、(2)に記載の組成物。
(4)前記合成樹脂がポリエステル樹脂、前記硬化剤がメラミン樹脂である、(2)に記載の組成物。
(5)(1)記載のセルロース複合体の平均粒径が、半径4cmの4枚パドル翼を取り付けたプロペラ攪拌機を用いて25℃、500rpmで20分間、水に分散させた固形分濃度1%の水分散液として測定した場合に10μm以下であり、且つ、該セルロース複合体のチクソトロピーインデックス(TI値)が固形分濃度を2%にした以外は上記と同様の条件で分散させた水分散液として測定した場合に4以上である、分散助剤(1)記載の組成物。
(6)セルロース複合体100質量部に対して分散助剤を50~3000質量部含む、(5)に記載の組成物。
(7)さらに合成樹脂及び添加剤を含む、(6)記載の組成物。
(8)前記合成樹脂が造膜性樹脂である、(7)記載の組成物。
(9)ウエットオンウエットで多層塗装し、焼き付けをする塗装方法であって、(1)~(8)のいずれかに記載の組成物を下層及び/又は上層に用いる、上記塗装方法。
(10)前記塗装方法が3コート1ベーク塗装である、(9)に記載の塗装方法。
(11)前記セルロース複合体の平均粒径が、半径4cmの4枚パドル翼を取り付けたプロペラ攪拌機を用いて25℃、500rpmで20分間、水に分散させた固形分濃度1%の水分散液を測定した場合に10μm以下であり、且つ、該セルロース複合体のチクソトロピーインデックス(TI値)が、固形分濃度を2%にした以外は上記と同様の条件で分散させた水分散液として測定した場合に4以上である、上記セルロース複合体を含む塗料用の添加剤。
特に、本発明の合成樹脂としては、アニオン型の合成樹脂が好ましい。カチオン型の合成樹脂の場合、ブツが発生しやすくなる場合がある。アニオン型合成樹脂の中でも、水性ポリエステル樹脂又は水性アルキド樹脂を用いることが好ましい。これらの樹脂はもちろん変性したもので構わない。
カーボネート類としては、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、エチレンカーボネート等が挙げられる。
<セルロース複合体の平均粒径>
(1)試料の濃度1質量%になるようにエクセルオートホモジナイザー(日本精機株式会社製、ED-7型)で、15000rpmで5分間分散した。
(2)レーザー回折散乱装置(堀場製作所製 LA-910)により積算体積が50%になる値を読み取り平均粒径とした。
<酸価の測定>
試料1g(固形分換算)を精密にはかりとり、水約200mlを加えて溶かした。これに0.05mol/l硫酸5mlをピペットで加え、10分間、95℃で加熱したのち、室温まで冷却して、フェノールフタレイン指示薬を加え、0.1mol/l水酸化カリウムで滴定した。同時に空試験も行いその差から酸成分を中和に必要な水酸化カリウム量(mg)として算出した。
<平均分子量>
GFCカラムを用いて常法により分析した。
<顔料分散組成物及び塗料組成物の評価方法>
・貯蔵安定性
試作サンプル50gをガラス製サンプル瓶に秤り取り、このサンプルを25℃、50℃の恒温室に7日間放置後、サンプル瓶を静かに取り出して、下記評価基準により経時安定性を評価した。
◎(優):沈降分離が見られず、初期と変化が見られない。
○(良):若干沈降分離が見られるが、初期とほとんど変化が見られない。
△(可):沈降分離により上澄みが確認されるが、嵩高い沈降となっている。
×(不可):沈降分離により完全に上澄みが確認でき、完全に沈降している。
・再分散性
上記、7日間放置後のサンプルをおよそ10cmの振り幅で2回/秒のスピードで振ったあとの状態を観察した。
○(良):11秒~60秒振れば貯蔵前の状態に戻る。
△(可):60秒振っても、壁面への固着は取れるが、わずかに凝集物が残る。
×(不可):60秒振っても、壁面への固着が残る、若しくは明らかに凝集物が残る。
・色別れ防止
上記の放置後のサンプルを再分散性評価時と同様の条件で2回振った後の色別れの状態を目視で観察した。
△(可):若干色別れしている。
×(不可):完全に色別れしている。
・タレ(塗工性)
水性塗料組成物をスプレーガンにより、みがき鋼板に塗装し、焼付を行い、その塗膜の状況をみてタレを評価した。
○(良):吹き付け時には全くタレはなく、焼付時に極僅かにタレが見られる。
△(可):吹きつけ時に若干タレる。
×(不可):完全にタレを生じて塗膜にムラができる。
・ワキ(平滑性)
各実施例の条件にて塗膜化した塗膜を以下の基準で目視評価した。
△(可):やや劣る(ラウンドあり)
×(不可):不良(肌荒れ、オレンジピール)
・仕上がり外観
ウエットオンウエット塗装した場合と、各層焼き付けした場合を目視で比較した。
△(可):若干、塗膜に違いがあるように見える。
×(不可):明らかに両塗装方法の塗膜が違う。
・耐塩性
試験塗板を塗面上にカッターでクロスカットキズを入れてJIS-Z-2371(orJIS-K5600)の塩水噴霧試験に192時間(1000hr)放置し、錆の発生状況を観察した。
△(可):部分的に錆が発生
×(不可):全面的に錆が発生
・耐候性試験
JIS K5600に準じて、耐候性を1000時間実施した。試験後には、下記の評価試験を行った。
A)鉛筆硬度試験
JIS K5600に準じて、塗膜面に鉛筆を押し当てて、塗膜の硬度を調査した。
△(可):試験前と比較して、硬度に1ランクの変化が認められる。
×(不可):試験前と比較して、硬度に2ランク以上の変化が認められる。
*1ランクとは例えば硬度がHから2Hに変化することである。
B)付着力試験
ASTM D-3359に準じて、塗膜に碁盤目を入れ粘着テープを密着させ直ぐ剥がしたときの付着力を調査した。
△(可):部分的に剥離が認められる。
×(不可):全面的に剥離が認められる。
〔経時安定性の評価方法〕
得られた各インキを蓋付き透明容器(30ml)に収容して、50℃の恒温槽に保管して2週間放置後、静かに容器を取り出して、下記評価基準により経時安定性を評価した。
評価基準:
◎(優):沈降分離が見られず、初期と変化が見られない。
○(良):若干沈降分離が見られるが、初期とほとんど変化が見られない。
△(可):沈降分離により上澄が確認されるが、嵩高い沈降となっている。
×(不可):沈降分離により完全に上澄が確認でき、完全に沈降している。
〔粘度経時安定性の評価方法〕
各インキを室温(25℃)以下に3時間以上放置して室温(25℃)まで冷却し、B形粘度計を用いて25℃における60rpmの粘度を測定し、下記評価基準で評価した。なお、初期インキ粘度も同様(25℃、60rpm)にして測定したものである。
評価基準:
◎(優):初期からの粘度変化が±2%未満
○(良):初期からの粘度変化が±2%以上~5%未満
△(可):初期からの粘度変化が±5%以上~10%未満
×(不可):初期からの粘度変化が±10%以上
<チクソトロピーインデックス(TI値)>
(1)固形分濃度が2%、総量1300~1700mlの水分散液となるようにサンプルと純水を2Lステンビーカーに量り取り、汎用攪拌翼かい十字(半径35mm)を取り付けたプロペラ攪拌機(スリーワンモーターHEIDON(商品名)BL-600)を用いて25℃、500rpmで20分間分散した。
(2)25℃の雰囲気中に3時間静置した。
(3)回転粘度計(株式会社トキメック製、B形粘時計、ローターNo.1)をセットし、セット後30秒後にローターの回転を開始し、それから30秒後の指示置より粘度を算出した。ローター回転数は6rpm、60rpmの順番で測定した。この時得られた、6rpmでの粘度の値を、60rpmでの粘度の値で割ったものがチクソトロピーインデックス(TI値)である。
<易分散性セルロース複合体の平均粒径>
(1)試料の濃度1質量%にてTI値を求める際と同様に分散液を調製した。
(2)レーザー回折散乱装置(堀場製作所製 LA-910)により積算体積が50%になる値(メジアン径)を読み取り平均粒径とした。
(実施例1及び比較例1、2)
エチレングリコール20.5質量部、トリメチロールプロパン12.9質量部、無水フタル酸51.7質量部を加え、180℃で5時間エステル化反応を行い、さらに無水トリメリット酸14.9質量部を加えて180℃で1時間反応させて、ポリエステル樹脂を得た。これにメラミン樹脂(サイメル254、三井サイテック(株)製)をポリエステル樹脂/メラミン樹脂=70/30(固形分比)となるように添加した。60℃で一時間攪拌し、トリエチルアミンにて中和した。そのまま60℃で15分攪拌し、固形分が40質量%になるように脱イオン水をゆっくりと添加し、水性ワニスAを得た。
(実施例2及び比較例3、4)
市販のDPパルプを裁断し、0.6質量%塩酸下において、121℃で60分間、加水分解処理を行った。得られた酸不溶性残渣を純水にて濾過洗浄を行い、結晶性セルロースのウエットケークを得た。このウエットケークの固形分に対して、酸価9.5、数平均分子量が2×106である水溶性高分子のキサンタンガムと、デキストリンを、結晶性セルロース/キサンタンガム/デキストリンの比率が75/5/20(固形分質量比)となるように加えて、ニーダーにて混練・磨砕を行い、乾燥、粉砕して、セルロース複合体Bを得た。
(実施例3及び比較例5)
市販のDPパルプを裁断し、0.5質量%塩酸下において、115℃で60分間、加水分解処理を行った。得られた酸不溶性残渣を純水にて濾過洗浄を行い、結晶性セルロースのウエットケークを得た。このウエットケークの固形分に対して、酸価2、重量平均分子量が5×104である水溶性高分子のカルボキシメチルセルロースナトリウムを、結晶性セルロース/カルボキシメチルセルロースナトリウムの比率が89/11(固形分質量比)となるように加えて、ニーダーにて混練・磨砕を行い、乾燥、粉砕して、セルロース複合体Cを得た。このセルロース複合体C0.5質量部、赤色酸化鉄40質量部、脱イオン水59部を混合し、SGミルで分散・混合し、顔料分散組成物C(固形分41質量%)を得た。
(実施例4及び比較例6)
市販のDPパルプを裁断し、0.65質量%塩酸下において、126℃で60分間、加水分解処理を行った。得られた酸不溶性残渣を純水にて濾過洗浄を行い、結晶性セルロースのウエットケークを得た。このウエットケークの固形分に対して、酸価2、重量平均分子量が5×104である水溶性高分子のカルボキシメチルセルロースナトリウムと、酸価9.5、数平均分子量が2×106である水溶性高分子のキサンタンガムとデキストリン及び食用油脂(菜種油)を、結晶性セルロース/カルボキシメチルセルロースナトリウム/キサンタンガム/デキストリン/食用油脂(菜種油)の比率が73/5/2.8/19/0.2(固形分質量比)となるように加えて、ニーダーにて混練・磨砕を行い、乾燥、粉砕してセルロース複合体Dを得た。そして、水系アルキッド樹脂(アクアブル48E、固形分50質量%、昭和ワニス(株)製)21.6質量部、二酸化チタン60.0質量部、脱イオン水9.9質量部、ジメチルエタノールアミン0.1質量部、セルロース複合体D0.3質量部をボールミルにて1時間分散し顔料分散組成物D(固形分85質量%)を得た。
(製造例1)
市販のDPパルプ(平均重合度850)を裁断し、1%塩酸下において、110℃、60分間、加水分解処理を行い、得られた酸不溶性残渣を純水にてろ過洗浄を行い、結晶性セルロースのウエットケークを得た。このウエットケークの固形分に対して、セルロース/キサンタンガム/デキストリンの比率が75/5/20(固形分質量比)となるようにキサンタンガム、デキストリンを加えて、ニーダーにて混練・磨砕を行った。得られたセルロース複合体のウエットケークを80℃の温水に、固形分濃度が15質量%になるように加え、分散させた。該分散液に、セルロース/トレハロースの比率が60/40(固形分質量比)になるようにトレハロースを加え、さらに20分間攪拌した。この分散溶解液を高圧ホモジナイザー(APV社製)を用いて15MPaの圧力で1パスして磨砕処理したのち、スプレードライヤーを用いて入り口温度が90~100℃、出口温度が70~80℃の条件で噴霧乾燥して、易分散性セルロース複合体αを得た。易分散性セルロース複合体αの分散液の平均粒径は7μmであり、TI値は4.2であった。
(製造例2)
60℃の温水10kgを用意し、軽く攪拌しながら、結晶性セルロース80質量%とカラヤガム10質量%とデキストリン10質量%からなる乾燥状態のセルロース複合体(セオラスRC-N81(商品名)、旭化成ケミカルズ(株)製)を0.5kg加えた後、デキストリン(パインデックス#3(商品名)、松谷化学工業(株)製)3kgを加え、さらに20分間攪拌した。この分散溶解液を高圧ホモジナイザー(APV社製)を用いて20MPaの圧力で1パスして磨砕処理したのち、スプレードライヤーを用いて入り口温度が90~100℃、出口温度が70~80℃の条件で噴霧乾燥して、易分散性セルロース複合体βを得た。易分散性セルロース複合体βの分散液の平均粒径は9μmであり、TI値は6.0であった。
(製造例3)
60℃の温水10kgを用意し、軽く攪拌しながら、結晶性セルロース80質量%とカラヤガム10質量%とデキストリン10質量%からなる乾燥状態のセルロース複合体(セオラスRC-N81(商品名)、旭化成ケミカルズ(株)製)を1.37kg加えた後、デキストリン(パインデックス#3(商品名)、松谷化学工業(株)製)1.13kgを加え、さらに20分間攪拌した。この分散溶解液を高圧ホモジナイザー(APV社製)を用いて15MPaの圧力で2パスして磨砕処理したのち、スプレードライヤーを用いて入り口温度が90~100℃、出口温度が70~80℃の条件で噴霧乾燥して、易分散性セルロース複合体γを得た。易分散性セルロース複合体γの分散液の平均粒径は8μmであり、TI値は6.1であった。
(製造例4)
市販のDPパルプ(平均重合度850)を裁断し、1%塩酸下において、110℃、60分間、加水分解処理を行い、得られた酸不溶性残渣を純水にてろ過洗浄を行い、結晶性セルロースのウエットケークを得た。このウエットケークの固形分に対して、セルロース/カルボキシメチルセルロースナトリウムの比率が89/11(固形分質量比)となるようにカルボキシメチルセルロースナトリウムを加えて、ニーダーにて混練・磨砕を行った。得られたセルロース複合体のウエットケークを80℃の温水に、固形分濃度が15質量%になるように加え、分散させた。該分散液に、セルロース/デキストリンの比率が60/40(固形分質量比)になるようにデキストリンを加え、さらに20分間攪拌した。この分散溶解液を高圧ホモジナイザー(APV社製)を用いて15MPaの圧力で1パスして磨砕処理したのち、スプレードライヤーを用いて入り口温度が90~100℃、出口温度が70~80℃の条件で噴霧乾燥して、易分散性セルロース複合体δを得た。易分散性セルロース複合体δの分散液の平均粒径は6μmであり、TI値は8.5であった。
<顔料分散組成物の調整>
(実施例5~8及び比較例7~10)
製造例1~4で得られた易分散性セルロース複合体及び、セルロース複合体α(セオラスRC-591(商品名)、旭化成ケミカルズ(株)製、本発明測定条件での平均粒径21μm、TI値2.9)、セルロース複合体β(セオラスRC-N81(商品名)、旭化成ケミカルズ(株)製、本発明測定条件での平均粒径38μm、TI値1.8)及び、セルロース複合体γ(特開2006-296302(文献8)の実施例1に開示されたセルロース複合体の易分散安定剤、平均粒径11μm、TI値3.9)を用いて顔料分散組成物を作成した。
J1~J4の顔料分散組成物は、貯蔵安定性、再分散性ともに良好であった。一方でH1~H3はいずれも顔料の沈降・分離が生じた。H3は食品分野においては十分な沈降安定性を与え得る易分散性はあるため、H1、H2よりは貯蔵安定性・再分散性は良好であったが、完全に保存前の状態に戻ることはなかった。H1、H2、H3はセルロース複合体を用いてはいるが、分散装置が高速インペラ-攪拌機では十分に分散できないため、機能を十分に発揮できなかった。H4では予備分散をしているため、貯蔵安定性は、本発明の易分散性セルロース複合体を用いたものと同等であったが、若干、色別れ防止機能が悪く色ムラを生じた。
(実施例9及び比較例11)
実施例8で得られた顔料分散組成物J4を用いて、下記の組成で水性塗料組成物を作製し評価した。塗膜の評価は、硅酸カルシウム板の試験板にアプリケーターにて塗布し110℃のオーブンで1時間乾燥して得られた塗膜について行った。各成分の混合は、高速インペラ-攪拌機で1000rpmで30分攪拌することにより行った。比較例11では顔料分散組成物J4を顔料分散組成物H1に置き換えて、他は同様の水性塗料を作製し評価した。その結果を表4に示す。
アクリル樹脂エマルション(合成樹脂;固形分40%) 100質量部
〔E410(旭化成ケミカルズ社製)〕
B.B.P(可塑剤) 2質量部
テキサノール(造膜助剤) 5質量部
実施例9に比べ、比較例11は、用いた顔料分散組成物と同じく貯蔵安定性、再分散性が悪いだけではなく、塗工性等までが悪化した。
(実施例10及び比較例12)
下記の組成で水性塗料を作製した。各成分の混合は、高速インペラ-攪拌機により1000rpmで30分攪拌した。比較例12は、実施例10の易分散性セルロース複合体γを、セルロース複合体β(セオラスRCN-81(商品名)、旭化成ケミカルズ(株)製、本発明測定条件での平均粒径38μm、TI値1.8)に置き換えて同様に実施した。塗膜の評価は、得られた塗料組成物を市販の試験板に塗布し、140℃で20分処理したものを用いて行った。その評価結果を表5に示す。
〔エリーテルKZA-1734(ユニチカ社製)〕
顔料分散ペースト 13質量部
〔SF611 ホワイト(東洋インク社製)、固形分量73%〕
硬化剤 (固形分80質量%) 15質量部
〔ポリアミン系硬化剤(アンカマイド502)〕
易分散性セルロース複合体γ 1質量部
〔SW -17(シンロイヒ社製)、固形分量42%〕
造膜性樹脂:アクリロニトリル・ブタジエン共重合体の水分散液60質量%
〔Nipol LX517A(日本ゼオン社製)、固形分量40%〕
尿素 18 重量%
分散安定剤:易分散性セルロース複合体β 2質量%
水(精製水)14質量%
上記配合成分をタンク内に撹拌しながら順次添加し、均一になるまで、高速インペラ-攪拌機1500rpmで混合撹拌した後に1μmのバグフィルターで濾過することによりインキを製造した。
(実施例12)
下記配合成分を下記方法により製造してインキを得た。
〔SW-14(シンロイヒ社製、固形分量42%)〕
造膜性樹脂:スチレンブタジエン共重合樹脂の水分散体60質量%
〔Nipol LX438C(日本ゼオン社製)、固形分量45%〕
分散安定剤:易分散性セルロース複合体γ 1質量%
尿素 15質量%
水(精製水)20質量%
上記配合成分を、タンク内に撹拌しながら順次添加し、均一になるまで、高速インペラ-攪拌機1500rpmで混合撹拌した後、1μmのバグフィルターで濾過することによりインキを製造した。
(比較例13)
実施例12の易分散性セルロース複合体γをセルロース複合体αセオラスRC-591(商品名)、旭化成ケミカルズ(株)製、本発明測定条件での平均粒径21μm、TI値2.9)に置き換えて、他は同じ処方でインクを作成した。比較例13ではバグフィルターに多量の残渣が生じた。以上により得られたインクを前述の方法で評価した。その結果を表6に示す。
Claims (11)
- 顔料100質量部、セルロース複合体0.01~50質量部、及び水を含む組成物であって、該組成物の固形分が25質量%を超えて、かつ粘度が30mPa・S以上であり、並びに該セルロース複合体は、酸価2.0以上で且つ重量平均分子量が1×103~1×107の親水性高分子0.5~50質量%及び結晶性セルロース50~99.5質量%を含み、該セルロース複合体の平均粒径が10μm以下である、上記組成物。
- さらに合成樹脂及び硬化剤を含む、請求項1に記載の組成物。
- 前記合成樹脂がアニオン型合成樹脂である、請求項2に記載の組成物。
- 前記合成樹脂がポリエステル樹脂、前記硬化剤がメラミン樹脂である、請求項2に記載の組成物。
- 請求項1記載のセルロース複合体の平均粒径が、半径4cmの4枚パドル翼を取り付けたプロペラ攪拌機を用いて25℃、500rpmで20分間、水に分散させた固形分濃度1%の水分散液として測定した場合に10μm以下であり、且つ、該セルロース複合体のチクソトロピーインデックス(TI値)が固形分濃度を2%にした以外は上記と同様の条件で分散させた水分散液として測定した場合に4以上である、請求項1記載の組成物。
- セルロース複合体100質量部に対して分散助剤を50~3000質量部含む、請求項5に記載の組成物。
- さらに合成樹脂及び添加剤を含む、請求項6記載の組成物。
- 前記合成樹脂が造膜性樹脂である、請求項7記載の組成物。
- ウエットオンウエットで多層塗装し、焼き付けをする塗装方法であって、請求項1~8のいずれかに記載の組成物を下層及び/又は上層に用いる、上記塗装方法。
- 前記塗装方法が3コート1ベーク塗装である、請求項9に記載の塗装方法。
- セルロース複合体の平均粒径が、半径4cmの4枚パドル翼を取り付けたプロペラ攪拌機を用いて25℃、500rpmで20分間、水に分散させた固形分濃度1%の水分散液を測定した場合に10μm以下であり、且つ、該セルロース複合体のチクソトロピーインデックス(TI値)が、固形分濃度を2%にした以外は上記と同様の条件で分散させた水分散液として測定した場合に4以上である、上記セルロース複合体を含む塗料用の添加剤。
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