TW201728674A - Aqueous resin dispersion composition containing alkaline earth metal compound particles - Google Patents

Abstract

Provided is a novel resin composition which is imparted with the functionality of alkaline earth metal compound particles such as strontium carbonate particles. The present invention relates to an aqueous resin dispersion composition which contains alkaline earth metal compound particles and an aqueous resin dispersion.

Description

Aqueous resin dispersion composition containing alkaline earth metal compound particles

The present invention relates to an aqueous resin dispersion composition containing an alkaline earth metal compound particle and an aqueous resin dispersion.

In recent years, attempts have been made to produce various functional materials for various functional materials. In the case of the material used in the field of the electronic device or the optical field, for example, as shown in Patent Document 1, the alkaline earth metal compound is cerium carbonate, which is a dielectric ceramic powder such as barium titanate powder. The use of raw materials.

For example, barium titanate powder is produced by mixing strontium carbonate powder and titanium dioxide powder as a powder mixture, followed by firing. The dielectric ceramic powder is used as a constituent material of a dielectric ceramic layer of a laminated ceramic capacitor.

Further, Patent Document 2 discloses that in a specific polymer resin such as COP (cyclic polyolefin) or PMMA (polymethyl methacrylate), the direction (length direction) of the bonding chain of the polymer resin and the needle are The acicular strontium carbonate particles are dispersed in such a manner that the long-axis direction (longitudinal direction) of the cerium carbonate-like particles is parallel or at right angles to each other. It is recorded that it will be due to the bond of polymer resin The birefringence produced by the alignment of the chain is offset by the birefringence due to the alignment of the ruthenium particles, and becomes a non-birefringent optical resin material. Others, cesium carbonate is also known to have a function of radio wave absorption or radiation prevention, for example.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2011/052680

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-35347

As described in Patent Documents 1 to 2, strontium carbonate, which is an example of an alkaline earth metal compound, is considered as a constituent material of a dielectric ceramic layer of a laminated ceramic capacitor or an optical material for controlling optical properties, but it is expected to be more useful. expand.

In the present invention, it is intended to provide a novel resin composition which imparts functionality by alkaline earth metal compound particles such as cesium carbonate.

This aspect (1) relates to an aqueous resin dispersion composition containing an alkaline earth metal compound particle and an aqueous resin dispersion.

The present invention (2) relates to an aqueous resin dispersion composition according to the aspect (1), wherein the alkaline earth metal compound particles comprise cerium carbonate particles.

The present invention (3) relates to an aqueous resin dispersion composition according to the aspect (1) or (2), wherein the aqueous resin is a polyurethane resin.

The aqueous resin dispersion composition according to any one of the above aspects (1) to (3), wherein the aqueous resin dispersion composition is active At least one of an energy ray-curable composition and a thermosetting composition.

The aqueous resin dispersion composition according to any one of the above aspects (1) to (4), wherein the average length of the alkaline earth metal compound particles is 100 nm or less, and the alkaline earth metal compound particles The average aspect ratio is in the range of 1.0 to 5.0.

The aqueous resin dispersion composition according to any one of the above aspects (1) to (5), wherein the surfactant is applied to the surface of the alkaline earth metal compound particles.

The aqueous resin dispersion composition according to any one of the above aspects (1) to (6), wherein the alkaline earth metal is relative to the weight of the solid component of the aqueous resin dispersion composition The weight of the compound particles is 2.5% by mass or more.

The present invention (8) relates to a coating composition comprising the aqueous resin dispersion composition according to any one of the aspects (1) to (7).

The present invention (9) relates to a coating composition comprising the aqueous resin dispersion composition according to any one of the aspects (1) to (7).

The present invention (10) relates to an optical resin material containing the aqueous resin dispersion composition according to any one of the aspects (1) to (7).

The present invention (11) relates to a coating film which is formed from the aqueous resin dispersion composition according to any one of the aspects (1) to (7).

According to the present invention, it is possible to provide a novel resin composition which imparts functionality to an alkaline earth metal compound particle such as cesium carbonate.

[Fig. 1] A graph showing the relationship between the amount of cesium carbonate added and the out-of-plane birefringence.

Hereinafter, an aqueous resin dispersion composition containing an alkaline earth metal compound particle according to an embodiment will be described.

In the embodiment, the alkaline earth metal compound particles are mainly composed of an alkaline earth metal. The average long diameter of the alkaline earth metal compound particles is not particularly limited, but in the present case, the alkaline earth metal compound particles are defined, for example, as nanoparticles or fine particles having an average major axis of 500 nm or less.

Here, the average long diameter can be measured by visually or image-processing a scanning electron microscope (SEM) photograph of the alkaline earth metal compound particles. The long diameter of the alkaline earth metal compound particles can be measured, for example, as a length in the longitudinal direction (length of the long side) when the alkaline earth metal compound particles such as cerium carbonate particles are regarded as rectangular. In addition, the short diameter of the alkaline earth metal compound particles can be measured as the length in the short direction (the length of the short side) when the alkaline earth metal compound particles are regarded as a rectangle.

Specifically, in the image, a rectangle having the smallest area circumscribing the alkaline earth metal compound particles is calculated, and the long side and the short side are obtained from the lengths of the long side and the short side of the rectangle. Further, "average" means measuring the number of statistically reliable (N number) alkaline earth metal compound particles. The average value obtained by the child. The number (N number) is usually 300 or more, preferably 500 or more, and more preferably 1,000 or more.

Further, the average aspect ratio of the alkaline earth metal compound particles is not particularly limited, and may be, for example, in the range of 1.0 to 5.0.

Furthermore, the aspect ratio referred to herein means the "long diameter/short diameter" of the particles. Also, the average aspect ratio means the average of the aspect ratios. That is, the average aspect ratio is obtained by measuring the aspect ratio of a plurality of particles and calculating the average of the aspect ratios obtained from the plurality of particles. Further, the number of particles (N number) for calculating the average value is as described above.

Examples of the alkaline earth metal compound particles include carbonates, sulfates, nitrates, oxides, chlorides, hydroxides, and the like of an alkaline earth metal. Further, examples of the alkaline earth metal include calcium, barium, strontium, radium and the like. Therefore, examples of the alkaline earth metal compound particles include calcium carbonate particles, cerium carbonate particles, and cerium carbonate particles. The alkaline earth metal compound particles are preferably cerium carbonate particles from the viewpoints of various uses such as the use of radio wave absorption, the use of radiation prevention, and/or optical use.

Preferably, the cerium carbonate particles are adhered to a surfactant. Thereby, the dispersibility of the cerium carbonate particles in the resin composition or the solvent before being mixed in the resin composition can be improved.

The kind of the surfactant is not particularly limited, and is preferably an anionic surfactant. The anionic surfactant is more preferably a compound having a hydrophilic group and a hydrophobic group and having an anion group formed in water. The hydrophilic group is preferably a polyoxyalkylene group containing an oxygen alkyl group having 1 to 8 carbon atoms. The hydrophobic group is preferably an alkyl group or an aryl group. The alkyl group and/or the aryl group may also have a substituent. The number of carbon atoms of the alkyl group is preferably in the range of 3 to 30, more preferably 10 to 18. The aryl group may have a carbon number of 6 to 30. An anion group is formed in water, preferably selected from the group consisting of a carboxylic acid group (-COOH), a sulfate group (-OSO ₃ H), a phosphate group (-OPO(OH) ₂ , -OPO(OH)O-). At least one acid group of the group. The hydrogen atom contained in these acid groups may be substituted with an alkali metal ion or an ammonium ion such as sodium or potassium.

From the viewpoint of dispersibility of the cerium carbonate particles in the resin composition or the solvent before being mixed in the resin composition, the surfactant is preferably a polycarboxylic acid-based anionic surfactant or a polyphosphoric acid-based surfactant. Anionic surfactant. The surfactant is more preferably a polycarboxylic acid-based anionic surfactant from the viewpoint of further improving the dispersibility of the cerium carbonate particles in the aqueous medium.

The anionic surfactant of the polycarboxylic acid type may, for example, be a compound represented by the following formula (I).

(herein, "R ¹ " means a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. "E ¹ " means an alkylene group having a carbon number of 1 to 8. "a" It means a positive number in the range of 1 to 20, preferably 2 to 6. Further, "R ¹ " is preferably an alkyl group having 10 or more carbon atoms, preferably 10 to 18 carbon atoms.

Examples of the polyphosphoric acid-based anionic surfactant include a compound represented by the following formula (II) (monomer) and a compound represented by the following formula (III) (dimerization) a mixture of a compound represented by the formula (II) and a compound represented by the formula (III).

(herein, "R ² " means a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. "E ² " means an alkylene group having a carbon number of from 1 to 8. "b" It is a positive number in the range of 1 to 20, preferably 2 to 6. Further, "R ² " is preferably an alkyl group having 10 or more carbon atoms, preferably 10 to 18 carbon atoms.

("R ³ " and "R ⁴ ") means a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. "R ³ " and "R ⁴ " may also differ. "E ³ " And "E ⁴ " means an alkylene group in the range of 1 to 8 carbon atoms. "E ³ " and "E ⁴ " may also be different. "c" and "d" mean 1 to 20, preferably It is a positive number in the range of 2 to 6. "c" and "d" can also be mutually different. Further, "R ³ " and "R ⁴ " are both 10 or more carbon atoms, preferably 10~. An alkyl group within the range of 18 is preferred).

For the cerium carbonate particles, one type of surfactant may be used alone or two or more types of surfactants may be used in combination. Further, the surfactant may be attached to only one layer of the surface of the cerium carbonate particles, or may be attached to two or more layers. When two or more layers of the surfactant are attached, the same surfactant may be used for each layer, or different types of surfactant may be used for each layer. Further, whether or not a surfactant is adhered to the surface of the cerium carbonate particles can be confirmed by measuring the infrared absorption spectrum of the particle surface by using a Fourier transform infrared spectrometer (FT-IR).

The method for producing an alkaline earth metal compound particle according to the embodiment includes a step of preparing a dispersion (first dispersion) obtained by dispersing an alkaline earth metal compound in an aqueous solvent, and is used for improving in a solvent. In the presence of a particle-dispersible surfactant, shearing force is applied, and the primary particles are brought into contact with the surfactant while dispersing the primary particles of the alkaline earth metal compound in an aqueous solvent, thereby obtaining a dispersion (second dispersion) a dispersing step; and a drying step of heating and drying the second dispersion at a temperature of 100 to 300 ° C to obtain a powder. The method for producing the alkaline earth metal compound particles before the surface treatment is not particularly limited, and examples thereof include a method in which an alkaline earth metal compound as a raw material is reacted to form an aqueous slurry, and the mixture is aged.

Hereinafter, a step of producing cerium carbonate particles will be described as an example of the alkaline earth metal compound particles.

While stirring an aqueous solution or an aqueous suspension (hereinafter referred to as an aqueous slurry) of cerium hydroxide as a raw material, carbon dioxide gas is introduced in the presence of a crystal growth inhibitor such as tartaric acid to carbonate cerium hydroxide. Thereby, substantially spherical cerium carbonate particles having a small aspect ratio are produced.

Further, a method of producing substantially spherical cerium carbonate particles can be described in, for example, International Publication No. 2011/052680. Further, the particles can be grown into needle-shaped strontium carbonate particles by aging the substantially spherical strontium carbonate particles at a specific temperature and time.

Further, in order to impart high dispersibility in a solvent, a surfactant may be added to the cerium carbonate particles. In this case, for example, a surfactant is added to the aqueous slurry by applying a shearing force to the aqueous slurry after the ripening, such as a stirring blade mixer. Thereby, the primary particles containing the cerium carbonate particles are dispersed in the aqueous slurry, and the primary particles are brought into contact with the surfactant.

Then, the aqueous slurry obtained by the above method is dried by heating by a drying method using a thermal dryer such as a spray dryer to obtain a dried product of highly dispersible cerium carbonate particles.

The alkaline earth metal compound particles having high dispersibility in one embodiment are excellent in dispersibility when dispersed in a solvent, and thus can be used in various applications.

Next, the aqueous resin dispersion of one embodiment is not particularly limited, and preferably contains an aqueous resin composed of a polyurethane resin.

The composition of the polyurethane resin is not particularly limited. The polyurethane resin is preferably obtained from, for example, at least one of a polyester polyol, a polyether polyol, and a polycarbonate polyol. Further, since the durability (for example, light resistance, hydrolysis resistance, and the like) is excellent, the polyurethane resin is more preferably obtained from at least a polycarbonate polyol. Further, from the viewpoint of dispersion stability in an aqueous medium, etc., a polyurethane resin is preferred. It is obtained from at least a polyol compound (a) containing a polycarbonate polyol, a polyol (b) containing an acidic group, and a polyisocyanate (c).

The polyol compound (a) is not particularly limited as long as it contains a polycarbonate polyol. The polycarbonate polyol is a high molecular weight polyol in which a polyol monomer such as a diol is carbonate-bonded, and the number average molecular weight of the polycarbonate polyol is preferably from 400 to 8,000.

The polycarbonate polyol may be one obtained from one or more kinds of polyol monomers, a carbonate or phosgene. The polycarbonate polyol is preferably one or more kinds of polyol monomers and carbonates, from the viewpoint of easy production and the fact that the terminal chloride is not formed. Further, the polycarbonate polyol in the present embodiment may contain an ether bond or an ester bond which is equal to or less than the number of the average carbonate bond in one molecule.

The type of the polyol monomer constituting the polycarbonate polyol is not particularly limited, and examples thereof include an aliphatic polyol monomer, an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, and an aromatic group. Polyol monomer and the like. The various polyol monomers are not particularly limited, and for example, a diol described in International Publication No. 2010-098316 can be used.

The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate; aromatic carbonates such as diphenyl carbonate; and cyclic carbonates such as ethyl carbonate. Others may also be used to produce phosgene which is a polycarbonate polyol. From the viewpoint of easy production of a polycarbonate polyol, the carbonate is preferably an aliphatic carbonate, particularly preferably dimethyl carbonate.

The polyol compound (a) is not included as long as it contains a polycarbonate polyol. Special restrictions may also include other polyols. The other polyol is not particularly limited as long as it is a polyol different from the above polycarbonate polyol, and examples thereof include a polyether polyol and a polyester polyol, for example, a diol having a number average molecular weight of less than 400. . Further, as the other polyol, the polyol (b) containing an acidic group described later is not contained. The polyol compound (a) may be used singly or in combination of plural kinds.

The polyol (b) having an acidic group is one having two or more hydroxyl groups in one molecule and one or more acidic groups. Further, examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. The polyol (b) containing an acidic group, specifically, those described in International Publication No. 2010-098316 can be used. The polyol (b) containing an acidic group may be used singly or in combination of plural kinds.

The polyisocyanate compound (c) is not particularly limited, and examples thereof include an aromatic polyisocyanate, an aliphatic polyisocyanate, and an alicyclic polyisocyanate. From the viewpoint of obtaining a coating film which is not easily yellowed, etc., it is preferred to use an alicyclic polyisocyanate as the polyisocyanate compound (c). Here, specific examples of the various polyisocyanates include the compounds described in International Publication No. 2010-098316. Further, as the polyisocyanate compound (c), a diisocyanate compound having two isocyanate groups per molecule can be suitably used. These polyisocyanate compounds may be used singly or in combination of plural kinds.

The polyurethane resin is preferably obtained from a urethane prepolymer, and the urethane prepolymer is composed of the above polyol compound (a) and an acid group-containing polyol. (b), and the polyisocyanate compound (c) To. Such urethane prepolymers can be produced by various manufacturing methods. The method for producing the urethane prepolymer includes, for example, a method in which a mixture of the polyol compound (a) and the acidic group-containing polyol (b) is reacted with the polyisocyanate compound (c).

In the method for producing a urethane prepolymer, a urethane-based catalyst can be used. As such a urethane-based catalyst, for example, a catalyst described in International Publication No. 2010-098316 can be used.

The reaction of the polyol compound (a), the acidic group-containing polyol (b), and the polyisocyanate compound (c) as a constituent component can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl hydrazine, N-methylpyrrolidone, and N-ethyl. Pyrrolidone, ethyl acetate, and the like.

The method for producing the aqueous resin dispersion in the present embodiment is appropriately selected in accordance with the intended aqueous resin dispersion, and is not particularly limited. An example of such a production method is a method in which all of the raw materials are mixed, reacted, and dispersed in an aqueous medium to obtain an aqueous resin dispersion. Further, as another method, the polyol compound (a), the acidic group-containing polyol (b), and the polyisocyanate compound (c) may be reacted to obtain a urethane prepolymer, and then an amine may be obtained. The acidic group of the urethane prepolymer is neutralized, and the polyurethane prepolymer is dispersed in an aqueous medium, and the chain extender is reacted as it is, whereby an aqueous resin dispersion can be obtained.

In the present embodiment, a compound which is reactive with an isocyanate group of the urethane prepolymer may be used as a chain extender. So As the compound, for example, those described in International Publication No. 2010-004951 can be used. These compounds may be used alone or in combination of two or more.

In the aqueous resin dispersion of the present embodiment, the polyurethane resin of the aqueous resin is dispersed in the aqueous medium. Examples of the aqueous medium include water or a mixed medium of water and a hydrophilic organic solvent. Examples of the water include purified water, ion-exchanged water, distilled water, ultrapure water, and the like. It is preferable to use ion-exchanged water as the aqueous medium in consideration of the easiness of obtaining or prevention of the particles from becoming unstable due to the influence of the salt. Examples of the hydrophilic organic solvent include lower monohydric alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as ethylene glycol and glycerin; N-methylmorpholine, dimethyl hydrazine, and dimethylformamide; An aprotic hydrophilic organic solvent such as N-methylpyrrolidone. The amount of the hydrophilic organic solvent in the aqueous medium is preferably from 0 to 20% by weight.

In addition to the alkaline earth metal compound particles and the aqueous resin dispersion, the aqueous resin composition dispersion may contain a resin different from the aqueous resin dispersion and harden it, in addition to the effect of the present invention. Agents, additives, etc.

The above aqueous resin may be an active energy ray-curable resin or a thermosetting resin. Examples of the active energy ray include a particle beam such as an electron beam, and an electromagnetic wave such as X-ray or ultraviolet ray. The resin is preferably an ultraviolet curable resin from the viewpoint of ease of handling and production cost.

The resin itself may have curability, but the resin composition may also contain a constituent component which hardens the resin. The resin composition, for example, as a constituent component for imparting ultraviolet curability, may suitably contain photoradical polymerization properties depending on the purpose. A component or a photoionic polymerizable component.

An example of a component which imparts ultraviolet curability is an acrylic monomer or an acrylic oligomer. Specific examples thereof include a polyfunctional oligomer having a (meth) acrylonitrile group, a polyfunctional monomer having three or more (meth) acryl fluorenyl groups in one molecule, and a (meth) acrylonitrile group. 1~2 functional monomer.

Examples of the polyfunctional oligomer having a (meth) acrylonitrile group include polyester (meth) acrylate, polyurethane (meth) acrylate, (meth) acrylate epoxy ester, and the like. .

Examples of the polyfunctional monomer having three or more (meth) acrylonitrile groups in one molecule include trimethylolpropane tri(meth)acrylate and di-trimethylolpropane tetra(methyl). Acrylate, tris(meth)acrylate, cis ((meth)acryloxyethyl) isocyanate, cis ((meth)acryloxypropyl) isocyanurate, pentaerythritol tris (a) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(methyl) ) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol VIII (methyl) ) Acrylate and the like.

Examples of the 1-2-functional monomer having a (meth)acryl fluorenyl group include cyclohexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and (methyl). Benzyl acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclo(meth)acrylate Anthracene ester, isodecyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, (A) a monofunctional (meth) acrylate monomer such as ethoxyethoxyethyl acrylate, phenoxyethyl (meth) acrylate or phenoxypropyl (meth) acrylate; (Meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, diethylene glycol di(meth) acrylate, three Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate , bisphenol A di(meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide modified bisphenol A II 2-functional (meth) acrylate, neopentyl glycol modified trimethylolpropane di(meth) acrylate, bis-(2-methylpropenyloxyethyl) phthalate ( Methyl) acrylate monomer.

The resin composition may further contain an additive such as a tackifier, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and a sedimentation inhibitor, as needed. One type of additive may be used alone, or a plurality of additives may be used in combination. Further, these additives can be used in an amount which is generally used in the range.

In the aqueous resin dispersion, the solid content is preferably from 1 to 70% by weight, more preferably from 5 to 50% by weight based on the total of the aqueous resin dispersion. The solid content of the aqueous resin dispersion refers to a component which is applied as a coating film after the aqueous resin dispersion is applied to a substrate, dried, and crosslinked by light irradiation or/and heating. Thus, the aqueous medium or neutralizing agent is not included in the solid component.

<Method of Forming Coating Film>

By dispersing the alkaline earth metal compound particles in a solvent such as water and adding the aqueous resin dispersion composition to the solvent, the aqueous resin dispersion composition containing the alkaline earth metal compound particles can be formed by stirring for a specific period of time. The coating liquid formed. A coating film containing an aqueous resin composition of an alkaline earth metal compound particle can be formed on a transparent substrate by applying a coating liquid onto a transparent substrate and drying the coating liquid to remove the solvent.

The coating method of the coating liquid may be any method. Examples of the coating method include a T-die method, a doctor blade method, a bar coating method, a roll coating method, a lip coating method, and the like.

As a result of the inventors of the present invention, it has been found that the aqueous resin dispersion composition containing the alkaline earth metal compound particles such as cesium carbonate can provide a novel aqueous resin dispersion composition imparting functionality and The obtained coating film. Further, it should be noted that the composition of the coating film is the same as the composition of the solid component of the aqueous resin dispersion composition.

In particular, as a result of intensive studies by the inventors of the present invention, it has been found that the adhesion of the coating film can be improved by including the alkaline earth metal compound particles in the aqueous resin. Further, since the alkaline earth metal compound particles have high dispersibility to the aqueous resin dispersion composition, the transparency and haze of the coating film containing the aqueous resin composition can be maintained.

The average long diameter of the alkaline earth metal carbonate particles is 500 nm or less, preferably 10 to 100 nm, more preferably 15 to 75 nm, still more preferably 20 to 50 nm. When the average long diameter is less than 10 nm, the particles are too small to be easily aggregated, and the dispersibility is liable to lower. On the other hand, the average long diameter exceeds At 500 nm, when the particles are too large, when mixed with a resin, transparency is liable to lower.

It is preferred to impart the above surfactant to the surface of the alkaline earth metal compound particles. In this case, even when the average long diameter of the alkaline earth metal compound particles is small, the alkaline earth metal compound particles have high dispersibility in the aqueous resin dispersion. Thereby, the transparency or haze of the coating film can be maintained. Further, by dispersing the alkaline earth metal compound particles to which the surfactant is added to the aqueous resin dispersion composition, the adhesion of the coating film can be further improved.

The type of the aqueous resin is as described above, and more preferably a polyurethane resin. The aqueous polyurethane resin is excellent in light resistance, weather resistance, and heat resistance. Therefore, it is suitable as a coating film for optical films.

The average aspect ratio of the alkaline earth metal carbonate fine particles is not particularly limited, and is usually in the range of 1.0 to 5.0, preferably 2.0 to 4.5, more preferably 2.5 to 4.0. When the average aspect ratio is more than 5.0, the fine particles become too long and are easily broken, which tends to cause a decrease in the particle size distribution. Further, when the aspect ratio is too small, it may be difficult to exert an effect on the birefringence control of the optical film.

The coating film obtained from the above aqueous resin dispersion composition can also be suitably used as an optical film. Since the optical film contains fine and highly dispersed alkaline earth metal carbonate fine powder, it is excellent in transparency, and the birefringence of the optical film can be adjusted by adjusting the content of the alkaline earth metal carbonate powder to the entire optical film.

For example, the polyurethane resin exhibits positive intrinsic birefringence, but an optical film having negative birefringence may be formed by adding alkaline earth metal carbonate particles to the polyurethane resin.

[Examples]

Next, examples will be described, but the present invention is not limited to the following examples.

(Example 1) (Production Example of Aqueous Resin Dispersion)

In a reaction apparatus equipped with a stirrer and a heater, the polyol component is a polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol with a carbonate (ETERNACOLL (registered trademark) UC100; manufactured by Ube Industries; Number average molecular weight 1030) 160g, number average molecular weight 2030 polytetramethylene ether glycol (PTMG) 18.7g, 2,2-dimethylolpropionic acid 22.1g, and hydrogenated MDI 147g, N-methyl-2 In 146 g of pyrrolidinone (NMP), in the presence of 0.2 g of dibutyltin dilaurate, it was heated at 80 to 90 ° C for 6 hours in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 2.11% by weight. The reaction mixture was cooled to 80 ° C, and among them, 16.7 g of triethylamine was added/mixed, 330 g was taken out, and it was added to 622 g of water under strong stirring. Next, 46.7 g of a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added to obtain an aqueous polyurethane resin dispersion (aqueous resin dispersion).

(surface treatment of nano particles)

A water slurry having an average long diameter of 35 nm and an average aspect ratio of 2.1 cerium carbonate particles of 5 mass% and 300 g was placed in a 300 mL beaker, and 8 mass% of a polycarboxylic acid copolymer type surfactant was added to the solid content (hereinafter, This is called "surfactant 1") and stirred with a stirrer for 5 minutes. The slurry solution was stirred using Clearmix (manufactured by M-Technique Co., Ltd.) for 20 minutes. Thereafter, the apparatus was stopped, and the water slurry was collected to obtain a 5% SrCO ₃ dispersion containing 8 mass% of a polycarboxylic acid copolymer type surfactant with respect to the mass of the cerium carbonate particles.

(Manufacturing method of adding SrCO ₃ doping liquid)

To 10 g of the aqueous resin dispersion obtained in the production example, 6 g of the above dispersion liquid 1 and 0.03 g of a leveling agent BYK-345 (manufactured by BYK Co., Ltd.) were added to a self-rotating revolution mixer (Thinky Awatori chain Taro ARE-310) Disperse for 4 minutes to obtain a doping solution A to which SrCO ₃ was added.

Here, the weight of the cerium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of the cerium carbonate particles in the polyurethane film to be described later is 10% by mass.

(Polyurethane film forming method)

The doping liquid A to which SrCO _{3 was} added was applied to a polyethylene terephthalate (hereinafter referred to as "PET") film to have a wet film thickness of 150 μm. It was dried at 60 ° C for 60 minutes and dried at room temperature for 3 days. This was heat-treated at 120 ° C for 120 minutes to obtain a polyurethane film A.

(transmittance measurement)

The visible light transmittance of the polyurethane film A peeled off from PET was measured using a spectrophotometer (manufactured by JASCO Corporation). The results are shown in Table 1.

(Example 2)

In addition to the above-mentioned method for producing a doping liquid to which SrCO ₃ is added, 0.3 g of cerium carbonate particles (powder) obtained by drying the dispersion liquid used in Example 1 is added, in place of the cerium carbonate particle dispersion liquid, The above methods are the same. The resulting polyurethane film was B. The visible light transmittance of the polyurethane film B was measured in the same manner as in Example 1. The results are shown in Table 1.

Here, the weight of the cerium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of the cerium carbonate particles in the polyurethane film was 10% by mass.

As a result of the results of the first and second examples, it is understood that the aqueous polyurethane resin dispersion in which the cerium carbonate particles are added even when the cerium carbonate particles are in the state of a water slurry or a powder, is formed into a film formed film. Transmittance is high and transparent. Therefore, the aqueous polyurethane resin dispersion composition containing cerium carbonate particles has functional properties such as radio wave absorption performance or radiation prevention, optical property control, etc., which can be used in automobiles, and can be used in automobiles. Paint field (paint composition) or coating of synthetic resin molded body such as packaging, mobile phone case, home appliance case, personal computer case, decorative film, optical film (optical resin material), floor material, etc. cloth The agent (coating agent composition) can be used for various purposes such as radiation shielding materials.

(Example 3) (Production Example of Aqueous Resin Dispersion)

In a reaction apparatus equipped with a stirrer and a heater, the polyol component is a polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol with a carbonate (ETERNACOLL (registered trademark) UC100; manufactured by Ube Industries; Number average molecular weight 1030, 160 g), polytetramethylene ether glycol (number average molecular weight 2030, 18.7 g), 2,2-dimethylolpropionic acid (22.1 g), and hydrogenated MDI (147 g), in N Ethyl-2-pyrrolidone (146 g) was heated at 80 to 90 ° C for 6 hours in a nitrogen atmosphere in the presence of 0.2 g of dibutyltin dilaurate. The NCO group content at the end of the urethanization reaction was 2.11% by weight. The reaction mixture was cooled to 80 ° C, and triethylamine (16.7 g) was added/mixed thereto, and added to water (661 g) with vigorous stirring. Next, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (72.9 g) was added/mixed to obtain an aqueous polyurethane resin dispersion.

(surface treatment of nano particles)

A water slurry having a concentration of 10% by mass of cerium carbonate particles was placed in a 300 mL beaker, and a carboxylic acid-based anionic surfactant (hereinafter referred to as "the surfactant 2") was added to the solid component in an amount of 35 mass%. Stir for 5 minutes with a stir bar. This slurry solution was stirred for 20 minutes using Clearmix (manufactured by M-technique Co., Ltd.). Thereafter, the apparatus was stopped, and the water slurry was recovered to obtain a SrCO ₃ dispersion.

(Manufacturing method of adding SrCO ₃ doping liquid)

To 10 g of the aqueous resin dispersion obtained in the production example, 6 g of the above dispersion liquid 1 and 0.03 g of a leveling agent BYK-345 (manufactured by BYK Co., Ltd.) were added to a self-rotating revolution mixer (Thinky Awatori chain Taro ARE-310) Disperse for 4 minutes to obtain a doping solution to which SrCO ₃ was added.

Here, the weight of the cerium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of the cerium carbonate particles in the polyurethane film to be described later is 10% by mass.

On the polyethylene terephthalate (PET) substrate, the doping solution to which SrCO _{3 was} added was applied to have a wet thickness of 40 μm. After the addition of the doping solution of SrCO _{3 was} applied, it was immediately dried at 60 ° C for 90 minutes. Thereafter, it was allowed to stand at room temperature for 1 night. Thereby, a polyurethane film is formed on the PET substrate.

(Test method for adhesion)

The adhesion of the polyurethane film (polyurethane resin composition) to the PET substrate was tested by a 100-square test of the checkerboard peeling test/crosscut (JIS K5600) method. The polyurethane film on the PET substrate was cut (divided) into 100 squares, the cellophane tape was followed, and the cellophane tape was peeled off to determine the polyaminocarboxylic acid remaining on the PET substrate. The number of ester film sheets. Here, the 1 grid is set to a size of 2 mm × 2 mm.

The test results are shown in Table 2. In Table 2, the remaining side after the test is described. Number of grids.

(Example 4)

The same procedure as in Example 3 was carried out except that the weight of the cerium carbonate particles in the solid content in the aqueous resin dispersion composition was 20% by mass based on the weight of the cerium carbonate particles in the polyurethane film.

The adhesion test was carried out in the same manner as in Example 3. The test results are shown in Table 2.

(Example 5)

The same procedure as in Example 3 was carried out except that the weight of the polyurethane resin composition was 20% by mass based on the weight of the doping liquid to which SrCO ₃ was added.

The adhesion test was carried out in the same manner as in Example 3. The test results are shown in Table 2.

(Example 6)

In addition to changing the surfactant to be added to the cerium carbonate particles to a phosphate-based anionic surfactant (hereinafter referred to as "the surfactant 3"), and adding 30% by mass to the solid component, 3 is the same.

The adhesion test was carried out in the same manner as in Example 3. The test results are shown in Table 2.

(Example 7)

The same procedure as in Example 5 was carried out except that the surfactant added to the cerium carbonate particles was changed to the surfactant 3.

The adhesion test was carried out in the same manner as in Example 3. The test results are shown in Table 2.

(Comparative Example 1)

The same procedure as in Example 3 was carried out except that the cerium carbonate particles were not added to the aqueous resin dispersion.

The adhesion test was carried out in the same manner as in the examples. The test results are shown in Table 2.

(Comparative Example 2)

The same procedure as in Example 5 was carried out except that the cerium carbonate particles were not added to the aqueous resin dispersion.

The adhesion test was carried out in the same manner as in the examples. The test results are shown in Table 2.

From the results of the adhesion test, it is known that the amine group containing cerium carbonate particles The acid ester resin composition (urethane film) has high adhesion to the substrate.

(Example 8) (Production Example of Ultraviolet Curing Waterborne Resin Dispersion)

In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgKOH/g; polyol component is 1,4-ring Hexanediol: 1,6-hexanediol = 3:1 molar ratio of polyol mixture obtained by reacting carbonate with polycarbonate diol, 125 g), 2,2-dimethylolpropionic acid ( 22.4g), with isophorone diisocyanate (120g), in N-ethylpyrrolidone (100g), in the presence of dibutyltin dilaurate (0.2g), heated at 80-90 ° C under nitrogen atmosphere 3.5 hour. The reaction mixture was cooled to 80 ° C, and triethylamine (17.0 g) was added/mixed. The reaction mixture was added/mixed with a mixture of trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA) (weight ratio 1:1, 55.6 g), and added to water under strong stirring (661 g) )in. Next, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (69.4 g) was added/mixed. IRGACURE 500 (photopolymerization initiator, 17.3 g, manufactured by BASF Corporation) was added to the obtained solution, and the mixture was stirred until uniform, and an ultraviolet curable aqueous polyurethane resin dispersion was obtained.

(surface treatment of nano particles)

A cerium carbonate particle dispersion liquid was obtained in the same manner as in Example 1 except that the concentration of the cerium carbonate particles was 10% by mass.

(Manufacturing method of doping liquid containing cerium carbonate particles)

60 g of the above-mentioned dispersion liquid 1 and 0.3 g of the leveling agent BYK-345 (manufactured by BYK Co., Ltd.) were added to 100 g of the aqueous resin dispersion obtained in the production example, and the autotransformation mixer (Thinky Awatori chain Taro ARE-310) was added. Disperse for 3 minutes and defoam for 1 minute to obtain a doping solution to which SrCO ₃ was added.

Here, the weight of the cerium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of cerium carbonate in the polyurethane film described later is 10% by mass.

(Polyurethane film forming method)

The doping liquid to which SrCO _{3 was} added was applied onto a polyethylene terephthalate (hereinafter referred to as "PET") film, and dried at 60 ° C for 3 hours. The coating film was peeled off from the PET substrate, and further dried at 60 ° C for 2 hours to obtain a polyurethane film.

(Measurement of visible light transmittance and haze measurement)

The visible light transmittance and haze of the obtained polyurethane film were measured using a spectrophotometer (manufactured by JASCO Corporation).

(Measurement of out-of-plane birefringence)

The out-of-plane phase difference (thickness) of the polyurethane film was measured using a phase measuring device (KOBRA-WR manufactured by Oji Scientific Instruments Co., Ltd.) The phase difference of the direction; the hysteresis value in the thickness direction) Rth.

The phase measuring device is an in-plane phase difference (hysteresis value) R0 measured by light incident perpendicularly to the object to be measured (polyurethane film), and is incident on the object to be measured at an incident angle θ. The phase difference (hysteresis value) Rθ measured by the light, the thickness d (input value) of the object to be measured, and the average refractive index N _avr (input value) of the object to be measured are used to calculate the out-of-plane phase difference Rth. Further, the incident angle θ was 40°, and the wavelength of light was 547.4 nm.

The average refractive index N _avr , which means the average value of the refractive indices in the three directions orthogonal to each other, is defined by "N _{avr =} (Nx + Ny + Nz) / 3". Here, Nx, Ny, and Nz mean the refractive indices of the objects to be measured in the X-axis direction, the Y-axis direction, and the Z-axis direction, respectively. In this specification, the X-axis direction is the direction of the slow axis. The Y-axis direction is the direction of the fast axis. The Z-axis direction is the thickness direction of the object to be measured. In Example 8, the average refractive index of the polyurethane film was assumed to be 1.5050.

In general, the out-of-plane phase difference Rth is defined by the following equation: Rth = (Nx + Ny) / 2 - Nz) × d. Here, "d" means the thickness of the object to be measured. The out-of-plane birefringence value ⊿P was calculated from the value of the measured out-of-plane phase difference Rth. The out-of-plane birefringence value ⊿P is calculated by the following equation: ⊿P=Rth/d. Further, the thickness d of the measurement object can be measured by a micrometer.

The measurement results are shown in Table 3.

(Example 9)

The same procedure as in Example 8 was carried out except that the polyurethane film of Example 8 was dried and irradiated with an ultraviolet light having a cumulative light amount of 1000 mJ/cm ² .

(Embodiment 10)

(Manufacturing method of adding SrCO ₃ doping liquid)

In the same manner as in Example 9, except that 120 g of the above-mentioned dispersion liquid and 120 g of the leveling agent BYK-345 (manufactured by BYK) were added in an amount of 100 g of the aqueous resin dispersion obtained in the above-mentioned production example.

In the case of Example 10, the weight of the cerium carbonate particles in the solid content in the aqueous resin dispersion composition was 20% by mass. That is, the weight of the cerium carbonate particles in the polyurethane film was 20% by mass.

(Example 11)

The same procedure as in Example 9 was carried out except that the polyurethane film of Example 10 was dried and irradiated with an ultraviolet light having a cumulative light amount of 1000 mJ/cm ² .

(Comparative Example 3)

A film was obtained in the same manner as in Example 8 except that cerium carbonate particles were not added.

(Comparative Example 4)

A film was obtained in the same manner as in Example 9 except that cerium carbonate particles were not added.

Further, Fig. 1 is a graph showing the relationship between the value of the out-of-plane birefringence value ⊿P and the amount of cerium carbonate particles added.

When the solid content of the aqueous resin dispersion composition, that is, the concentration of the cerium carbonate particles in the entire optical film is about 10% by weight, it is understood that the out-of-plane birefringence ⊿P of the optical film becomes a negative value. Further, at this time, the in-plane birefringence ΔNxy≒0 can provide an optical film of a positive C plate. For example, in order to achieve high contrast in the oblique direction of the liquid crystal display device such as the IPS mode, as the phase difference plate, various combinations of a positive A plate and a positive C plate are used, and an optical film of the positive C plate can be provided. In this case, it should be noted that depending on the application, an optical film having a positive C plate is necessary in design.

Further, even when cerium carbonate particles were added, the haze of the optical film was maintained at less than 3%, and the visible light transmittance was maintained at 90% or more. In this way, an optical film having high transparency can be provided while controlling the birefringence value.

Further, the inventors of the present invention found that the haze of the optical film after ultraviolet curing is lower than that of the optical film before ultraviolet curing.

Here, referring to the graph shown in Fig. 1, it is known that even ultraviolet curing When the concentration of the solid component of the aqueous resin dispersion composition, that is, the concentration of the cerium carbonate particles in the entire optical film is 2.5% by weight or more, the optical composition may be used as the optical film. The out-of-plane birefringence ⊿P is a negative value.

The present invention has been described in detail with reference to the embodiments and embodiments thereof. It is obvious to those skilled in the art that the present invention is not limited to the embodiments and examples described herein. The present invention can be implemented with modifications and variations without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the description of the specification is intended to be illustrative, and is not intended to limit the invention.

Claims (11)

An aqueous resin dispersion composition comprising an alkaline earth metal compound particle and an aqueous resin dispersion. The aqueous resin dispersion composition of claim 1, wherein the alkaline earth metal compound particles comprise cerium carbonate particles. The aqueous resin dispersion composition of claim 1 or 2, wherein the aqueous resin is a polyurethane resin. The aqueous resin dispersion composition according to any one of claims 1 to 3, wherein the aqueous resin dispersion composition is at least one of an active energy ray-curable composition and a thermosetting composition. The aqueous resin dispersion composition according to any one of claims 1 to 4, wherein the alkaline earth metal compound particles have an average major axis of 100 nm or less, and the alkaline earth metal compound particles have an average aspect ratio of 1.0 to 5.0. The aqueous resin dispersion composition according to any one of claims 1 to 5, wherein a surfactant is provided on the surface of the alkaline earth metal compound particles. The aqueous resin dispersion composition according to any one of claims 1 to 6, wherein the weight of the solid earth component of the aqueous resin dispersion composition is 2.5% by mass or more based on the weight of the solid earth metal compound particles. A coating composition comprising the aqueous resin dispersion composition according to any one of claims 1 to 7. A coating composition comprising any one of claims 1 to 7 The aqueous resin dispersion composition of the item. An optical resin material containing the aqueous resin dispersion composition according to any one of claims 1 to 7. A coating film formed from the aqueous resin dispersion composition according to any one of claims 1 to 7.