JP6962777B2 - Dispersed resin composition and its uses - Google Patents

Description

The present invention relates to a dispersed resin composition and its use.

Conventionally, a propylene-based random copolymer modified with a chlorinated polyolefin resin having excellent adhesiveness, an unsaturated carboxylic acid, and / or an acid such as an anhydride thereof with a poorly adhesive polyolefin base material such as polypropylene or polyethylene. Polymers have been used as adhesive imparting agents. Also in the automobile industry, an adhesive-imparting agent for adhering a poorly adhesive paint to the polyolefin of the base material (in the automobile industry, a paint directly applied on the base material, which is composed mainly of the adhesive-imparting agent). This is particularly referred to as a primer coating material), and a propylene-based random copolymer modified with an acid such as the above-mentioned chlorinated polyolefin resin, unsaturated carboxylic acid and / or its anhydride has been used.

In the coating of such a plastic material made of polyolefin, a method of forming a multi-layer coating film of primer coating-water-based base coating-clear coating is generally performed. In such coating, after performing primer coating and water-based base coating, the next layer is formed wet-on-wet without heat curing in a single layer, and after forming a multi-layer coating film, all of them are performed. Is known as a curing method for heating a primer at a time (see Patent Documents 1 and 2).

In the formation of such a multi-layer coating film, if a mixed layer of the coating films occurs, the functionality of the obtained coating film is deteriorated and the appearance is deteriorated. Therefore, even in the case of wet-on-wet coating, it is necessary to remove the solvent to some extent by performing preheating after performing primer coating and water-based base coating in order to prevent layer mixing.

Japanese Unexamined Patent Publication No. 2011-240266 Japanese Unexamined Patent Publication No. 2009-173861 Japanese Unexamined Patent Publication No. 2016-87569

However, when such preheating is performed, a heating line and a subsequent cooling line are required in the painting line, which causes an increase in cost. Therefore, there is a demand for a method of coating a plastic material without preheating and without forming a mixed layer in a wet state. As such a method, for example, by blending a specific thickener or adjusting the blending amount of the volatile component of the paint, the viscosity of the primer coating film immediately before applying the base paint is increased. A method of suppressing layer mixing under preheatless conditions has been proposed by designing a primer coating material (see Patent Document 3). In the method of Patent Document 3, problems tend to occur in terms of paint stability, such as the primer coating tends to thicken over time.

Therefore, an object of the present invention is to provide a dispersed resin composition containing a modified polyolefin resin, which has thixotropic properties capable of suppressing the generation of mixed layers without preheating when used as a primer.

As a result of diligent studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by adding cellulose nanofibers to a dispersed resin composition containing a modified polyolefin resin and a dispersion medium. It came to be completed.
That is, the present inventors provide the following [1] to [11].
[1] A dispersed resin composition containing the following components (A) to (C).
Component (A): A polyolefin resin was modified with one or more polarity-imparting agents selected from the group consisting of unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and radically polymerizable monomers. Modified polyolefin resin.
Ingredient (B): Cellulose nanofibers.
Component (C): Dispersion medium.
[2] The dispersed resin composition according to the above [1], wherein the number ratio of agglomerates having an average particle size of 150 μm or more derived from the component (B) is less than 1%.
[3] The dispersed resin composition according to the above [1] or [2], wherein the component (A) is a chlorinated modified polyolefin resin obtained by modifying the polyolefin resin with the polarity-imparting agent and chlorine. ..
[4] The dispersed resin composition according to any one of the above [1] to [3], wherein the content of the component (B) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the component (A). ..
[5] The dispersed resin composition according to any one of the above [1] to [4], wherein the component (C) contains water or a hydrophilic substance.
[6] The polyolefin resin is at least one selected from the group consisting of a propylene homopolymer, an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer. The dispersed resin composition according to any one of the above [1] to [5], which comprises the polyolefin resin of the above.
[7] The dispersed resin composition according to any one of the above [1] to [6], wherein the modified weight of the component (A) by the polarity-imparting agent is 0.1 to 30% by weight.
[8] The dispersed resin composition according to any one of the above [1] to [7], wherein the weight average molecular weight of the component (A) is 10,000 to 500,000.
[9] A coating material containing the dispersed resin composition according to any one of the above [1] to [8].
[10] A primer coating material containing the dispersed resin composition according to any one of the above [1] to [8].
[11] A laminated coating film comprising a step of coating the primer coating according to the above [10] to form a wet-on primer layer, and a step of applying a topcoat coating on the wet-on primer layer and drying the coating. Forming method.

According to the present invention, it is possible to provide a dispersed resin composition containing a modified polyolefin resin, which has thixotropic properties capable of suppressing the generation of mixed layers without preheating when used as a primer.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.
In the present specification, the weight modified by the polarity-imparting agent in the modified polyolefin resin is also referred to as "graft weight".

[1. Dispersed resin composition]
The dispersed resin composition of the present invention comprises one or more selected polarity-imparting agents consisting of component (A): unsaturated carboxylic acid, derivative of unsaturated carboxylic acid, anhydride of unsaturated carboxylic acid, and radically polymerizable monomer. It contains a modified polyolefin resin obtained by modifying the polyolefin resin using the component (B): cellulose nanofibers, and the component (C): dispersion medium.

[1-1. Component (A): Modified Polyolefin Resin]
The dispersed resin composition of the present invention contains the component (A): modified polyolefin resin as the first component.

<Polyolefin resin>
Examples of the polyolefin resin used for the component (A) include those obtained by copolymerizing ethylene or α-olefin using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst. Specifically, propylene homopolymers (polypropylene), ethylene-propylene copolymers, propylene-butene copolymers such as propylene-1-butene copolymers, ethylene-propylene-1-butene copolymers and the like. Examples of resins selected from ethylene-propylene-butene copolymers (hereinafter, these copolymers may be collectively referred to as “propylene-based copolymers”) can be exemplified. These resins may be used alone or in admixture of a plurality of resins.

As the polyolefin resin used for the component (A), a polyolefin resin having a melting point (Tm) of 60 to 165 ° C. by a differential scanning calorimeter (DSC) is preferable. When the melting point is 60 ° C. or higher, it is possible to prevent the dispersion resin composition from being deteriorated in solvent resistance and the like. When the melting point is 165 ° C. or lower, it is possible to prevent the adhesion to the substrate from being lowered.

By using the polyolefin resins listed above as the polyolefin resin used for the component (A), a dispersed resin composition having excellent dispersibility in the component (C): dispersion medium can be obtained. When it is desired to improve the baking property on a polyolefin base material, a polyolefin resin can be selected according to the baking temperature. Further, it is also possible to select a polyolefin resin according to the application such as a primer for automobile coating, an adhesive for heat sealing, and a binder for ink.

For example, when it is desired to obtain a dispersed resin composition for high-temperature baking (general baking temperature: 100 to 120 ° C.) for a primer for automobile coating, a polyolefin resin produced using a Ziegler-Natta catalyst or a metallocene catalyst can be used. preferable. Further, when it is desired to obtain a dispersed resin composition for baking treatment at a low temperature (general baking temperature: 60 to 100 ° C.), a polyolefin resin produced by using a metallocene catalyst is preferable. In general, the use of a polyolefin resin having a low melting point is superior in low-temperature baking property. In particular, a propylene-based random copolymer produced using a metallocene catalyst is excellent in low-temperature seizure property.

As the metallocene catalyst described above, known ones can be used. Specifically, a metallocene catalyst obtained by combining the components (1) and (2) described below and, if necessary, the component (3) is preferable.
-Component (1); A metallocene complex which is a transition metal compound of Group 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand.
-Component (2); ion-exchangeable layered silicate.
-Ingredient (3); organoaluminum compound.

The measurement of Tm by DSC can be performed under the following conditions, for example. Using a DSC measuring device (manufactured by Hitachi High-Tech Science), a sample of about 10 mg is melted at 200 ° C. for 5 minutes, and then cooled to -60 ° C. at a rate of 10 ° C./min for crystallization. Then, the melting peak temperature at the time of melting by raising the temperature to 200 ° C. at 10 ° C./min is measured, and the temperature is evaluated as Tm. In addition, Tm in the Example described later is a value measured under the said conditions.

The component composition of the polyolefin resin used for the component (A) is not particularly limited, but the propylene component is preferably 50 mol% or more, more preferably 60 mol% or more. When the propylene component is 50 mol% or more, it is possible to prevent the adhesion to the propylene substrate from being lowered.

The weight average molecular weight of the polyolefin resin used for the component (A) is preferably 10,000 to 500,000, more preferably 20,000 to 300,000, and further preferably 65,000 to 200,000. be. The weight average molecular weight, including the examples described later, is a value measured by gel permeation chromatography (GPC, standard substance: polystyrene). The weight average molecular weight of the component (A): modified polyolefin resin described below is preferably within the above range.
The GPC measurement includes, for example, the following conditions.
Measuring equipment: HLC-8320GPC (manufactured by Tosoh)
Eluent: Tetrahydrofuran Column: TSKgel (manufactured by Tosoh)

<Degeneration>
The component (A) is a modified polyolefin resin. The modified polyolefin resin means one obtained by modifying the above-mentioned polyolefin resin. The modification is carried out with one or more polarity-imparting agents selected from the group consisting of unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and radically polymerizable monomers. By modifying with these polarity-imparting agents, physical properties such as adhesiveness and gasohol resistance can be improved. The polarity-imparting agent may be used in combination of two or more.

The modified polyolefin resin may be further modified with chlorine in addition to the above-mentioned polarity-imparting agent, depending on the type of the polyolefin resin as the raw material resin. By modifying with chlorine, the polarity of the resin is imparted and the crystallinity is lowered, and the solubility in a polar solvent and the compatibility with other polar resins can be improved.

In the following description, the polyolefin resin modified with the above-mentioned polarity-imparting agent with respect to the polyolefin resin is generally referred to as a modified polyolefin resin. The resin obtained when modified with chlorine is a chlorinated modified polyolefin resin.

The unsaturated carboxylic acid means an unsaturated compound having a carboxyl group. The unsaturated carboxylic acid derivative means a mono or diester, a mono or diamide, an imide, or the like of the compound. The unsaturated carboxylic acid anhydride means the anhydride of the compound.
Examples of the unsaturated carboxylic acid, the derivative of the unsaturated carboxylic acid, and the anhydride of the unsaturated carboxylic acid include fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid, nadic acid and their anhydrides, fumaric acid. Methyl, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, Examples thereof include diethyl maleate, dipropyl maleate, dibutyl maleate, maleimide, and N-phenylmaleimide. Of these, itaconic anhydride and maleic anhydride are preferred. The unsaturated carboxylic acid, the derivative of the unsaturated carboxylic acid, and the anhydride of the unsaturated carboxylic acid can be used alone or in combination of two or more.

The graft weight of the unsaturated carboxylic acid, the anhydride of the unsaturated carboxylic acid and the derivative of the unsaturated carboxylic acid in the modified polyolefin resin is preferably 0.1% by weight or more, more preferably 1% by weight or more. When it is 0.1% by weight or more, it becomes easy to form the dispersed resin composition of the aqueous dispersion, and the adhesiveness of the dispersed resin composition of the aqueous dispersion to the polar adherend can be maintained. The upper limit of the graft weight is preferably 20% by weight or less, more preferably 10% by weight or less. When it is 20% by weight or less, it is preferable because the generation of unreacted substances can be prevented, the adhesiveness to the non-polar adherend can be maintained, and these effects can be economically realized. The graft weight in the modified polyolefin resin is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight.

When only a compound selected from the group consisting of an unsaturated carboxylic acid, a derivative of an unsaturated carboxylic acid, and an anhydride of an unsaturated carboxylic acid is used as the polarity imparting agent, the following can be said. If the graft weight is less than the above-mentioned preferable range, the polarity of the dispersed resin composition may be lowered, and the solubility in an organic solvent may be lowered. On the other hand, if the graft weight is too large, a large amount of unreacted material may be generated or the adhesiveness to the non-polar adherend may be lowered, which is not preferable.
The graft weight of the unsaturated carboxylic acid, the derivative of the unsaturated carboxylic acid, and the anhydride of the unsaturated carboxylic acid can be determined by alkali titration method or Fourier conversion infrared spectroscopy. The numerical value of the graft weight shown in the examples described later is a numerical value measured by the alkaline titration method.

The radically polymerizable monomer means a (meth) acrylic compound or a vinyl compound. The (meth) acrylic compound is a compound containing at least one (meth) acryloyl group (meaning an acryloyl group and / or a meta-acryloyl group) in the molecule.
Examples of radically polymerizable monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and glycidyl (meth). ) Acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( Meta) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, ( Meta) Acryloylmorpholine, n-butylvinyl ether, 4-hydroxybutylvinyl ether, dodecylvinyl ether and the like. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, and lauryl (meth) acrylate are preferable, and methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and lauryl methacrylate are more preferable. The radically polymerizable monomer may be used alone or in combination of two or more, and the mixing ratio thereof can be freely set.

The (meth) acrylic compound preferably contains at least one compound selected from the (meth) acrylic acid ester represented by the following general formula (I) in an amount of 20% by weight or more. When the (meth) acrylic compound is used, the molecular weight distribution of the modified polyolefin resin can be narrowed, and the solvent solubility of the modified polyolefin resin and the compatibility with other resins can be further improved.
CH ₂ = CR ¹ COOR ² ... (I)
(In the general formula (I), R ¹ = H or CH ₃ , R ² = C _n H _{2n + 1} , n = 1 to 18 integers)
Here, n in the ^{R 2} in the general formula (I) is preferably 8 to 18 integer.

The graft weight of the radically polymerizable monomer in the modified polyolefin resin is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight. When only a radically polymerizable monomer is used as the polarity imparting agent, the following can be said. If the graft weight is less than 0.1% by weight, the solubility of the modified polyolefin resin, compatibility with other resins, and adhesive strength may decrease. Further, when the graft weight is more than 30% by weight, the reactivity is high, so that an ultrahigh molecular weight substance is formed and the solvent solubility is deteriorated, or the amount of homopolymer or copolymer not grafted on the polyolefin skeleton is increased. It is not preferable because it may occur.

The graft weight of the radically polymerizable monomer can be determined by Fourier transform infrared spectroscopy or 1H-NMR.

<Chlorination>
When a chlorinated modified polyolefin resin is used as the modified polyolefin resin, the chlorine content in the chlorinated modified polyolefin resin is not particularly limited, but is preferably 2 to 35% by weight, more preferably 4 to 25% by weight. By weight%. When it is 2% by weight or more, it is possible to prevent the solubility in an organic solvent from being lowered while ensuring the adhesiveness to various non-polar substrates. Further, when it is 35% by weight or less, it is possible to prevent the adhesiveness to various non-polar substrates from being lowered.

The chlorine content can be measured according to JIS-K7229. That is, it can be measured by using an "oxygen flask combustion method" in which a chlorinated modified polyolefin resin is burned in an oxygen atmosphere, the generated gaseous chlorine is absorbed by water, and the amount is quantified by titration.

When a chlorinated modified polyolefin resin modified with chlorine is used as the component (A), the total modified weight of the modified polyolefin resin is preferably 0.1 to 45% by weight, more preferably 1 to 30% by weight. 3 to 30% by weight is more preferable. When the modified weight is 0.1% by weight or more, it is possible to prevent the solubility of the chlorinated modified polyolefin resin and the compatibility with other resins from being lowered. Further, when the modified weight is 45% by weight or less, it is possible to prevent the adhesiveness from being lowered.

When a modified polyolefin resin that does not use chlorine is used as the component (A), the total modified weight of the modified polyolefin resin is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight. , 0.1 to 10% by weight is more preferable. When the modified weight is 0.1% by weight or more, it is possible to prevent the modified polyolefin resin from being less soluble and compatible with other resins. Further, when the modified weight is 30% by weight or less, it is possible to prevent the adhesiveness from being lowered.

The total modified weight of the modified polyolefin resin means the total amount of the chlorine content and the graft weight of the polarity imparting agent when chlorine is used, and when chlorine is not used, the graft of the polarity imparting agent is used. It means the total amount of weight.

The chlorinated modified polyolefin resin obtained when chlorine is used is usually deteriorated with dehydrochloric acid when exposed to ultraviolet rays or high heat. When the chlorinated-modified polyolefin resin is deteriorated by dehydrochloric acid, the working environment may be deteriorated by the liberated hydrochloric acid, including deterioration of physical properties such as deterioration of adhesion to a base material such as polypropylene material as well as coloring of the resin. Therefore, it is preferable to add a stabilizer.
The amount of the stabilizer added is preferably 0.1 to 5% by weight with respect to the resin component (solid content) in order to obtain the above effects. As the stabilizer, an epoxy compound can be exemplified, and among them, an epoxy compound compatible with the chlorinated modified polyolefin resin is preferable. A preferable example of such an epoxy compound is an epoxy compound having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups in one molecule.

Examples of such epoxy compounds include epoxidized soybean oil and epoxidized linseed oil in which a vegetable oil having a natural unsaturated group is epoxidized with a peracid such as peracetic acid; oleic acid, tall oil fatty acid, soybean oil fatty acid and the like. Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids in the above; epoxidized alicyclic compounds typified by epoxidized tetrahydrophthalate; Ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc.) can be mentioned. Also represented by butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, phenol polyethylene oxide glycidyl ether and the like. The monoepoxy compounds to be used are also mentioned. One type of these epoxy compounds may be used, or two or more types may be used in combination.
The stabilizers include metal soaps such as calcium stearate and lead stearate, organic metal compounds such as dibutyltin dilaurate and dibutylmalate, and hydrotalcites, which are used as stabilizers for polyvinyl chloride resin. Can also be used.

The method for obtaining a modified polyolefin resin by modifying the polyolefin resin with a polarity-imparting agent is not particularly limited. A known method can be used to graft-polymerize the polarity-imparting agent on the polyolefin resin to obtain a modified polyolefin resin. For example, a solution method in which a mixture of a polyolefin resin and a polarity-imparting agent is heated and dissolved in a solvent such as toluene and a radical generator is added, or a polyolefin resin, a polarity-imparting agent, using a Banbury mixer, a kneader, an extruder, or the like. Examples thereof include a method of obtaining a modified polyolefin resin by a melt-kneading method in which an ethylene α-olefin copolymer and a radical generator are added and kneaded. When one or more polarity-imparting agents selected from the group consisting of unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and radically polymerizable monomers are used as the polarity-imparting agents, these are collectively used. It may be added or added sequentially.
Here, the polyolefin resin can be appropriately selected and used from those listed as examples of the polyolefin resin.

Further, the order in which the polarity-imparting agent is graft-polymerized with the polyolefin resin is not particularly limited.

The radical reaction initiator that can be used in the reaction of graft-polymerizing the polarity-imparting agent on the polyolefin resin can be appropriately selected from known radical reaction initiators. In particular, organic peroxide compounds are preferable. For example, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1-bis (t). -Butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, Examples thereof include t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropylcarbonate and cumylperoxyoctate. Of these, dicumyl peroxide, di-t-butyl peroxide, and dilauryl peroxide are preferable.
The amount of the radical reaction initiator added to the polyolefin resin is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. If the amount of the radical reaction initiator added is less than this range, the graft polymerization rate may decrease. If the amount of the radical reaction initiator added exceeds this range, it is uneconomical.

When a polarity imparting agent selected from the group consisting of unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and radically polymerizable monomers is used, styrene, o-methylstyrene, p. -Methylstyrene, α-methylstyrene, divinylbenzene, hexadiene, dicyclopentadiene and the like may be added.

When chlorine is used in combination with one or more polarifiers selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated carboxylic acid anhydrides, and radically polymerizable monomers, the step of chlorinating is performed. It is preferable to do it last. That is, it is selected from the group consisting of an unsaturated carboxylic acid, a derivative of an unsaturated carboxylic acid, an anhydride of an unsaturated carboxylic acid, and a radically polymerizable monomer in the polyolefin resin by the above-mentioned solution method or melt-kneading method1. A method of graft-polymerizing a polarity-imparting agent of more than one species and then chlorinating by the method described later is preferable. The chlorination step is performed before graft polymerization with one or more polarifiers selected from the group consisting of unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and radically polymerizable monomers. This is usually not preferable because it may cause dehydrogenation during the graft polymerization reaction. However, as described below, if necessary, graft polymerization can be carried out by a low temperature solution method after chlorination.

When a compound having an ester such as a (meth) acrylic acid ester is used as the radically polymerizable monomer, the ester may be decomposed by chlorination. Therefore, when these compounds are used, it is preferable to carry out graft polymerization after the chlorination step.

As a method of chlorination, for example, a modified polyolefin resin obtained by graft-polymerizing a polarity imparting agent is dissolved in a solvent such as chloroform and then irradiated with ultraviolet rays or in the presence of the radical reaction initiator. A method of obtaining a chlorinated modified polyolefin resin by injecting the chlorinated polyolefin resin can be mentioned. Since the chlorine introduction rate changes depending on the type of polyolefin resin, reaction scale, reaction device, and other factors, the chlorine content can be adjusted while monitoring the amount of chlorine blown and the time.

The component (A) may be in the form of an aqueous dispersion or the like. The solid content concentration of the component (A) in the aqueous dispersion is preferably 10 to 50% by weight, more preferably 20 to 40% by weight.

The pH of the aqueous dispersion of the component (A) is preferably 5 or more, more preferably 6 to 11. When the pH is 5 or higher, neutralization is sufficiently performed, and component (A): the modified polyolefin resin does not disperse in other components, or even if dispersed, precipitation and separation are likely to occur over time, and storage stability is improved. It can be prevented from getting worse. Further, when the pH is 11 or less, compatibility with other components and work safety can be ensured.

The viscosity of the aqueous dispersion of the component (A) at 25 ° C. by a B-type viscometer is preferably 1 to 200 mPa · s, more preferably 1 to 100 mPa · s, and even more preferably 1 to 50 mPa · s.
The viscosity can be measured using a B-type viscometer, the rotation speed is 60 rpm, and a # 1 or # 2 rotor is used.

The average particle size of the component (A) is preferably 1 to 300 μm, more preferably 10 to 200 μm, and even more preferably 40 to 150 μm.
The average particle size can be measured using a Zetasizer 3000HS (manufactured by Sysmex Corporation).

[1-2. Ingredient (B): Cellulose Nanofiber (CNF)]
The dispersed resin composition of the present invention contains a component (B): cellulose nanofiber (CNF) as a second component. In the present specification, the cellulose nanofibers refer to fine fibers having a fiber width of about 2 to 500 nm and an aspect ratio of 10 or more. Cellulose nanofibers defibrate cellulose (hereinafter, also referred to as "chemically modified cellulose") that has been chemically treated (cationization: carboxylation (oxidation), carboxymethylation, esterification and other anionization: introduction of functional functional groups). Can be obtained by doing.

<Cellulose raw material>
Cellulose raw materials for producing chemically modified cellulose include, for example, vegetable materials (eg, wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp (conifer unbleached kraft pulp (NUKP), conifer bleached). Kraft Pulp (NBKP), Hardwood Unbleached Craft Pulp (LUKP), Hardwood Unbleached Craft Pulp (LBKP), Conifer Unbleached Sulfite Pulp (NUSP), Conifer Unbleached Sulfite Pulp (NBSP), Thermomechanical Pulp (TMP), Recycled Pulp, used paper, etc.)), animal materials (eg, squirrels), algae, microorganisms (eg, acetic acid bacteria (acetactor)), cellulose fibers originating from microbial products, etc. Can also be used. Cellulose fibers derived from plants or microorganisms are preferable, and cellulose fibers derived from plants are more preferable.

<Carboxymethylation>
When carboxymethylated cellulose is used as the chemically modified cellulose, the carboxymethylated cellulose may be obtained by carboxymethylating the above-mentioned cellulose raw material by a known method, or a commercially available product may be used. In either case, the degree of carboxymethyl substitution of cellulose per anhydrous glucose unit is preferably 0.01 to 0.50. The following method can be mentioned as an example of a method for producing such carboxymethylated cellulose.
Carboxymethylated cellulose can be produced by using a cellulose raw material as a starting material, performing a mercerization treatment in the presence of a solvent having a mass of 3 to 20 times, and then carrying out an etherification reaction. As the solvent, for example, water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tertiary butanol and the like can be used alone or in combination of two or more. .. When the lower alcohol is mixed, the mixing ratio of the lower alcohol is 60 to 95% by mass.
As the mercerizing agent, an alkali metal hydroxide (for example, sodium hydroxide, potassium hydroxide) having a molar conversion of 0.5 to 20 times per anhydrous glucose residue as a starting material is used.
The starting material, the solvent, and the mercerizing agent are mixed, and the mercerization treatment is carried out at a reaction temperature of 0 to 70 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Then, a carboxymethylating agent (for example, sodium monochloroacetate) is added per glucose residue in an amount of 0.05 to 10.0 times in terms of molars, and the reaction temperature is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction is carried out. Carboxymethylated cellulose can be produced by carrying out an etherification reaction for 30 minutes to 10 hours, preferably 1 hour to 4 hours.

<Carboxylation>
When carboxylated (oxidized) cellulose is used as the chemically modified cellulose, carboxylated cellulose (also referred to as oxidized cellulose) can be obtained by carboxylating (oxidizing) the above-mentioned cellulose raw material by a known method. Although not particularly limited, at the time of carboxylation, the amount of carboxyl groups should be adjusted to 0.6 to 2.0 mmol / g with respect to the absolute dry mass of the carboxylated cellulose nanofibers. Is preferable, and it is more preferable to adjust the concentration to 1.0 to 2.0 mmol / g.

As an example of the carboxylation (oxidation) method, a cellulose raw material is oxidized in water using an oxidizing agent in the presence of an N-oxyl compound and a compound selected from the group consisting of bromide, iodide or a mixture thereof. There are ways to do this. This oxidation reaction, carbon atoms having a C6 position of the primary hydroxyl group of the glucopyranose ring of the cellulose surface is selectively oxidized, and an aldehyde group on the surface, a carboxyl group (-COOH) or carboxylate groups - and ^(-COO) A chemically modified cellulose having, can be obtained. The concentration of the cellulose raw material at the time of the reaction is not particularly limited, but is preferably 5% by mass or less.

The N-oxyl compound is a compound capable of generating a nitroxy radical. As the N-oxyl compound, any compound can be used as long as it is a compound that promotes the desired oxidation reaction. For example, 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) and its derivative (for example, 4-hydroxy TEMPO) can be mentioned.

The amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing the cellulose raw material. For example, 0.01 to 10 mmol is preferable, 0.01 to 1 mmol is more preferable, and 0.05 to 0.5 mmol is further preferable with respect to 1 g of an absolute dry cellulose raw material. Further, it is preferably about 0.1 to 4 mmol / L with respect to the reaction system.

The bromide is a compound containing bromine, and examples thereof include an alkali metal bromide that can be dissociated and ionized in water. The iodide is a compound containing iodine, and examples thereof include alkali metal iodide. The amount of bromide or iodide used can be selected within a range in which the oxidation reaction can be promoted. The total amount of bromide and iodide is, for example, preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, still more preferably 0.5 to 5 mmol, based on 1 g of an absolute dry cellulose raw material.

As the oxidizing agent, known ones can be used, and for example, halogen, hypohalogenic acid, subhalogenic acid, perhalogenic acid or salts thereof, halogen oxide, peroxide and the like can be used. Of these, sodium hypochlorite, which is inexpensive and has a low environmental impact, is preferable. The appropriate amount of the oxidizing agent used is, for example, preferably 0.5 to 500 mmol, more preferably 0.5 to 50 mmol, still more preferably 1 to 25 mmol, still more preferably 3 to 10 mmol, based on 1 g of an absolute dry cellulose raw material. More preferred. Further, for example, 1 to 40 mol is preferable with respect to 1 mol of the N-oxyl compound.

In the oxidation step of the cellulose raw material, the reaction proceeds efficiently even under relatively mild conditions. Therefore, the reaction temperature is preferably 4 to 40 ° C, and may be room temperature of about 15 to 30 ° C. As the reaction progresses, carboxyl groups are generated in the cellulose, so that the pH of the reaction solution is lowered. In order to allow the oxidation reaction to proceed efficiently, it is preferable to add an alkaline solution such as an aqueous sodium hydroxide solution to maintain the pH of the reaction solution at 8 to 12, preferably about 10 to 11. Water is preferable as the reaction medium because it is easy to handle and side reactions are unlikely to occur.

The reaction time in the oxidation reaction can be appropriately set according to the degree of progress of oxidation, and is usually about 0.5 to 6 hours, for example, about 0.5 to 4 hours.

Further, the oxidation reaction may be carried out in two steps. For example, by oxidizing the oxidized cellulose obtained by filtration after the completion of the first-stage reaction again under the same or different reaction conditions, the efficiency is not affected by the reaction inhibition by the salt produced as a by-product in the first-stage reaction. Can be oxidized well.

As another example of the carboxylation (oxidation) method, there is a method of oxidizing by contacting a gas containing ozone with a cellulose raw material. By this oxidation reaction, the hydroxyl groups at at least the 2nd and 6th positions of the glucopyranose ring are oxidized, and the cellulose chain is decomposed. Ozone concentration in the ozone containing gas is preferably ^{50~250g / m 3, 50~220g / m} 3 and more preferably. The amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by mass, more preferably 5 to 30 parts by mass, when the solid content of the cellulose raw material is 100 parts by mass. The ozone treatment temperature is preferably 0 to 50 ° C, more preferably 20 to 50 ° C. The ozone treatment time is not particularly limited, but is about 1 to 360 minutes, preferably about 30 to 360 minutes. When the ozone treatment conditions are within these ranges, it is possible to prevent the cellulose raw material from being excessively oxidized and decomposed, and the yield of oxidized cellulose becomes good.
After the ozone treatment, the additional oxidation treatment may be performed using an oxidizing agent. The oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfate, and peracetic acid. For example, the additional oxidation treatment can be performed by dissolving these oxidizing agents in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and immersing the oxidized cellulose in the solution.

The amount of carboxyl groups of cellulose oxide can be adjusted by controlling the reaction conditions such as the amount of the oxidizing agent added and the reaction time described above.

<Cationation>
When cationized cellulose (hereinafter, also referred to as "cationized cellulose") is used as the chemically modified cellulose, glycidyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrialkylammonium hydrite or its halohydrin is used as the above-mentioned cellulose raw material. Cation by reacting a cationizing agent such as a mold with an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) as a catalyst in the presence of water and / or an alcohol having 1 to 4 carbon atoms. Chemicalized cellulose can be obtained. In this method, the degree of cation substitution per glucose unit of the obtained cationized cellulose is determined by controlling the amount of the cationizing agent to be reacted and the composition ratio of water and / or an alcohol having 1 to 4 carbon atoms. Can be adjusted.

The degree of cation substitution of the cationized cellulose per glucose unit is preferably 0.02 to 0.50. By introducing a cationic substituent into the cellulose raw material, the celluloses are electrically repelled from each other. Therefore, the cationized cellulose into which a cation substituent is introduced can be easily nano-defibrated. When the degree of cation substitution per glucose unit is 0.02 or more, nano-defibration can be sufficiently performed due to the electrical repulsion between celluloses. On the other hand, when the degree of cation substitution per glucose unit is 0.50 or less, swelling or dissolution can be suppressed, and a situation in which nanofibers cannot be obtained can be prevented. In order to efficiently perform defibration, it is preferable to wash the cationized cellulose obtained above.

<Esterification>
When cellulose having a phosphoric acid group introduced is used as the chemically modified cellulose, a cellulose having a phosphoric acid group introduced can be obtained by reacting a cellulose raw material with a compound having a phosphoric acid group. Compounds having a phosphoric acid group include phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and phosphorus. Examples thereof include tripotassium acid, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate and the like. The compound having a phosphoric acid group may be used alone or in combination of two or more. The amount of the compound having a phosphoric acid group added to the cellulose raw material is preferably 0.1 to 500 parts by mass, more preferably 1 to 400 parts by mass in terms of phosphorus element with respect to 100 parts by mass of the solid content of the cellulose raw material. 2 to 200 parts by mass is more preferable.

<Defibration>
The apparatus used for defibrating the chemically modified cellulose is not particularly limited, but an apparatus such as a high-speed rotary type, a colloid mill type, a high-pressure type, a roll mill type, and an ultrasonic type can be used. For defibration, a physical defibration treatment in which a strong shearing force is applied to an aqueous dispersion of chemically modified cellulose is preferable. In particular, in order to efficiently defibrate, it is preferable to use a wet high-pressure or ultra-high-pressure homogenizer capable of applying a pressure of 50 MPa or more to the aqueous dispersion and applying a strong shearing force. The pressure is more preferably 100 MPa or more, still more preferably 140 MPa or more. Further, prior to the defibration and dispersion treatment with a high-pressure homogenizer, the aqueous dispersion may be pretreated, if necessary, using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. good.

The average fiber diameter of the cellulose nanofibers thus obtained is usually about 2 to 500 nm in terms of the length-weighted average fiber diameter, but is preferably 2 to 50 nm. The average fiber length is preferably 50 to 2000 nm, more preferably 100 to 1000 nm, in terms of length-weighted average fiber length.

Atomic force microscope (AFM) or transmission electron microscope (TEM) is used for the length-weighted average fiber diameter and the length-weighted average fiber length (hereinafter, also simply referred to as "average fiber diameter" and "average fiber length"). It is obtained by observing each fiber. The average aspect ratio of cellulose nanofibers is usually 10 or more, preferably 50 or more. The upper limit is not particularly limited, but is usually 1000 or less. The average aspect ratio can be calculated by the following formula.

Average aspect ratio = average fiber length / average fiber diameter

When the average fiber length of the cellulose nanofibers is 400 to 1000 nm, the dispersed resin composition of the present invention tends to exhibit thixotropic properties, but may be inferior in workability due to an increase in viscosity.

When the average fiber length of the cellulose nanofibers is 100 nm or more and less than 400 nm, the dispersed resin composition of the present invention has excellent workability because the increase in viscosity is small, but the expression of thixotropic property may be limited. ..

Therefore, as the cellulose nanofibers, it is also possible to appropriately combine two or more types of cellulose nanofibers having different average fiber lengths.

[1-3. Component (C): Dispersion medium]
The dispersed resin composition of the present invention contains a component (C): a dispersion medium as a third component.

The dispersion medium is not particularly limited as long as it uniformly disperses the component (A) and the component (B), and a hydrophilic or lipophilic dispersion medium can be used. However, when the component (B) that has not been hydrophobized is used, it is preferable that water or a hydrophilic substance is contained as the main component. The hydrophilic substance means a substance exhibiting hydrophilicity. The hydrophilic substance is preferably a polar substance in which the polyolefin resin or the modified polyolefin resin is insoluble. Specific examples thereof include alcohols, ketones, and ester-based hydrophilic substances. Preferred examples of such a hydrophilic substance include methanol, ethanol, isopropyl alcohol, and acetone. These may be used alone or in combination of a plurality of types. Further, the water may be tap water, distilled water, purified water or the like. The water temperature can be appropriately set according to the dispersibility and other conditions. For example, if the water temperature is too high, chlorine-modified chlorinated polyolefin resin may be dehydrochlorinated. If the water temperature is too low, the (chlorinated) modified polyolefin resin is difficult to dissolve, which may lead to poor emulsification. Therefore, it is preferable to adjust the water temperature in consideration of these points.

As the dispersion medium, two or more kinds may be used in combination as long as the effect of the present invention is not impaired. Further, if necessary, a dispersion medium in which a lipophilic substance is combined with a dispersion medium containing water or a hydrophilic substance as a main component may be used.

[1-4. Dispersed resin composition]
The dispersed resin composition of the present invention can be obtained by dispersing the above components (A) to (C) by a known dispersion method. For example, it can be obtained by dispersing the component (A) in the component (C), dispersing the component (B) in the component (C), and then stirring and mixing the respective dispersions.

In the dispersed resin composition of the present invention, the blending ratio of the component (B): cellulose nanofibers to 100 parts by weight of the component (A): modified polyolefin resin is preferably 0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight. 10 parts by weight is more preferable, and 0.01 to 5 parts by weight is further preferable.

The solid content concentration in the dispersed resin composition of the present invention is preferably 10 to 50% by weight, more preferably 20 to 40% by weight.

The pH of the dispersed resin composition of the present invention is preferably 5 or more, more preferably 6 to 11. When the pH is 5 or higher, neutralization is sufficiently performed, and component (A): the modified polyolefin resin does not disperse in other components, or even if dispersed, precipitation and separation are likely to occur over time, and storage stability is improved. It can be prevented from getting worse. Further, when the pH is 11 or less, compatibility with other components and work safety can be ensured.

The viscosity of the dispersed resin composition of the present invention can be measured with a B-type viscometer and can be used as a measure of thixotropy.

In the dispersed resin composition of the present invention, the number ratio of agglomerates having an average particle size of 150 μm or more derived from the component (B) is preferably less than 1%, and the number ratio of agglomerates having an average particle size of 100 μm or more is 1. It is more preferably less than%, and further preferably the number ratio of agglomerates having an average particle size of 10 μm or more is less than 1%. The lower limit of the number ratio of agglomerates is not particularly limited, and is preferably 0% (that is, not included).
In addition, "derived from the component (B)" includes not only the aggregate of the component (B) alone but also the composite aggregate of the component (B) and another component such as the component (A).

In order to reduce the number ratio of aggregates having an average particle size of 150 μm or more derived from the component (B) to less than 1% in the dispersed resin composition of the present invention, for example, a TK homogenizer (manufactured by Primix Corporation) is used at 3000 rpm /. Process for 15 minutes. By such treatment, a uniform dispersion resin composition in which the number ratio of agglomerates having an average particle size of 150 μm or more derived from the component (B) is less than 1%, preferably not contained, can be obtained.

Since the agglomerates are usually transparent, they are difficult to observe visually. Therefore, for example, it is possible to observe by an evaluation method having the following steps (1) to (3). It is preferable to perform such an observation a plurality of times because a more accurate number ratio of agglomerates can be determined. The multiple times is usually about 3 times.
Step (1): A step of preparing a dispersed resin composition having a solid content of 1.0% by mass.
Step (2): A step of adding a coloring material to the dispersed resin composition and stirring the mixture.
Step (3): A step of observing the dispersed resin composition to which the coloring material is added in a range of 3 mm × 2.3 mm with an optical microscope (magnification: 100 times).
The amount of the coloring material added is about 5 to 20% by weight in the dispersed resin composition to which the coloring material is added. The stirring conditions are not particularly limited, and the coloring material can be mixed under normal conditions. For example, it can be stirred for 1 minute using a vortex mixer or the like.

<Color material>
The coloring material is a material having a color such as white, black, blue, red, yellow, and green. In the present invention, a colored pigment or dye can be used as the coloring material. It is preferably ink.

<Colored pigment>
The colored pigment is a pigment having colors such as white, black, blue, red, yellow, and green, and its shape is not particularly limited such as plate-like, spherical, and scaly. Examples of colored pigments include inorganic pigments and organic pigments.
Inorganic pigments include carbon black, iron black, composite metal oxide black, zinc chromate, lead chromate, lead tan, zinc phosphate, vanadium phosphate, calcium phosphate, aluminum phosphate molybdenum, calcium molybdenate, aluminum tripolyphosphate. , Bismus oxide, Bismas hydroxide, Basic bismuth carbonate, Bismus nitrate, Bismus silicate, Hydrotalcite, Zinc powder, Mica iron oxide, Calcium carbonate, Barium sulfate, Alumina white, Silica, Keisou soil, Kaolin, Tarku, Clay, mica, barita, organic bentnite, white carbon, titanium oxide, zinc flower, antimony oxide, lithopon, lead white, perylene black, molybdenum red, cadmium red, red iron oxide, cerium sulfide, yellow lead, cadmium yellow, yellow iron oxide, Yellow clay, bismuth yellow, shena, amber, green clay, mars violet, ultramarine, dark blue, basic lead sulfate, basic lead silicate, zinc sulfide, antimony trioxide, calcium complex, phthalocyanine blue, phthalocyanine green, oak, aluminum Examples include powder, copper powder, brass powder, stainless steel powder, titanium oxide-coated mica, iron oxide-coated mica, zinc oxide, silver particles, anatase-type titanium oxide, iron oxide-based calcined pigment, conductive metal powder, and electromagnetic wave absorbing ferrite. can.
Organic pigments include quinacridone red, polyazo yellow, anthraquinone red, anthraquinone yellow, polyazo red, azolake yellow, berylene, phthalocyanine blue, phthalocyanine green, isoindolinone yellow, watching red, permanent red, parared, toluidine maroon, Examples thereof include benzidine yellow, first sky blue, and brilliant carmine 6B.
These pigments can be used alone or in combination of two or more.

The average particle size of the colored pigment is usually 10 μm or less, preferably 0.01 to 10 μm, and more preferably 0.03 to 1 μm. When the average particle size is 10 μm or less, preferably 1 μm or less, the dispersibility of the colored pigment is stable in the dispersed resin composition, so that evaluation becomes easy. On the other hand, although the lower limit is not limited, if the average particle size is smaller than 0.01 μm, colored pigments may enter the agglomerates, which may make it difficult to observe the agglomerates with an optical microscope. The average particle size is measured by a laser diffraction type particle size distribution measuring device (for example, Mastersizer 3000 or Zetasizer Nano ZS manufactured by Malvern). If the pigment is not spherical, the average value of the longest diameter is taken as the average particle size.

<Dye>
A dye is an organic dye that selectively absorbs or reflects visible light and has a unique color, and is dyed on fibers, pigments, or the like by an appropriate dyeing method. Examples of the dye include azo dyes, diphenyl and triphenylmethane dyes, azine dyes, oxazine dyes, thiazine dyes and the like.
These dyes may be used alone or in combination of two or more.

The dispersed resin composition of the present invention may contain components (A) to (C), and may contain any component such as a basic substance or a surfactant as long as the effects of the present invention are not impaired. You may.

By containing a basic substance, the dispersed resin composition of the present invention can neutralize the acidic component in the component (A): modified polyolefin resin and further enhance the dispersibility in water and hydrophilic substances. .. As basic substances, preferably sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, Examples thereof include N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholin and the like, and more preferably, ammonia, triethylamine and 2-amino. Examples thereof include -2-methyl-1-propanol, morpholin, N, N-dimethylethanolamine and the like. These may be used alone or in combination of a plurality of types. The amount of the basic substance used can be adjusted to an arbitrary amount according to the amount of the acidic component of the modified polyolefin resin. Generally, it is preferable that the pH of the dispersed resin composition is 5 or more, particularly preferably pH 6 to 11.

The emulsifier refers to an agent or additive added for the purpose of stabilizing the dispersion when dispersing the polyolefin resin or the modified polyolefin resin in water or a hydrophilic substance, and can also be rephrased as a surfactant. In the present invention, a surfactant can be used as needed, and either a nonionic surfactant or an anionic surfactant can be used. Nonionic surfactants are preferred because they have better water resistance of the emulsified dispersed resin composition.

Examples of the nonionic surfactant include polyoxyethylene polyhydric alcohol fatty acid esters such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples thereof include polyoxyethylene polyoxypropylene polyol, sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkyl alkanolamide, and polyalkylene glycol (meth) acrylate. Preferably, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine and the like can be mentioned.

As anionic surfactants, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, α-olefin sulfonates, methyl tauryl salts, sulfosuccinates, ether sulfonates, ether carboxylates, Examples thereof include fatty acid salts, sodium sulfonate formalin condensates, alkylamine salts, quaternary ammonium salts, alkylbetaines, alkylamine oxides and the like. Preferred examples include polyoxyethylene alkyl ether sulfate, sulfosuccinate and the like.

The amount of the surfactant (emulsifier) added to the dispersed resin composition of the present invention is generally 30% by weight or less, preferably 25% by weight or less, based on the component (A): modified polyolefin resin. If it exceeds 30% by weight, an excess amount of surfactant that forms an aqueous dispersion resin composition or more will be added, which will significantly reduce the adhesiveness and water resistance, and will have a thermoplastic effect when formed into a dry film. , It may be unfavorable because it causes a bleeding phenomenon or easily causes blocking. The lower limit of the amount of the surfactant added is not particularly limited, but it is better to be as small as possible, and it is not necessary to add the surfactant substantially.

The dispersed resin composition of the present invention may further contain a cross-linking agent depending on the application and purpose. The cross-linking agent means a compound that reacts with a hydroxyl group, a carboxyl group, an amino group or the like existing in a modified polyolefin resin, a surfactant, a basic substance or the like to form a cross-linked structure. The cross-linking agent itself may be water-soluble, or may be dispersed in water in some way. More specifically, blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, amino resins and the like can be mentioned. The method of adding the cross-linking agent is not particularly limited. For example, it can be added during the hydration step or after the hydration step.

In addition to the above, the dispersed resin composition of the present invention comprises an aqueous acrylic resin, an aqueous urethane resin, lower alcohols, lower ketones, lower esters, preservatives, leveling agents, antioxidants, as required. Any component such as a light stabilizer, an ultraviolet absorber, a dye, a pigment, a metal salt, and an acid can be blended.

[2. Use]
When used as a primer, the dispersed resin composition of the present invention has a thixotropic property that can suppress the generation of mixed layers without preheating. Therefore, the dispersed resin composition of the present invention can be suitably used as, for example, a coating material, particularly a primer coating material.

[3. Laminated coating film forming method]
The method for forming a laminated coating film of the present invention is a step of applying a primer coating material containing the dispersion resin composition of the present invention to form a wet-on primer layer, and a step of applying a top coat coating material on the wet-on primer layer and drying it. , Have. When the dispersed resin composition of the present invention is used as a primer, it has a thixotropic property that can suppress the generation of mixed layers without preheating. It can be prevented from occurring. Therefore, the painting line does not require a heating line and a subsequent cooling line, and cost increase can be prevented.
The wet-on-primer layer refers to a wet state in which preheating is not performed. Topcoat coating refers to water-based base coating and the like.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, the method for measuring the physical property value or the like is the measurement method described above. Further, "part" means a part by weight unless otherwise specified.

(Production Example 1-1: Production of aqueous dispersion of chlorinated modified polyolefin resin (1))
2.5 parts of maleic anhydride and 2 parts of dicumyl peroxide were added to 100 parts of a propylene-based random copolymer (about 97% propylene, about 3% ethylene, melting point: 125 ° C.) produced using a metallocene catalyst as a polymerization catalyst. The mixture was mixed and supplied to a twin-screw extruder having L / D = 60 and φ = 40 mm using a quantitative feeder. The reaction was started with a residence time of 15 minutes and a barrel temperature of 180 ° C. (3rd to 7th barrels), and the pressure was reduced in the 9th barrel to remove unreacted maleic anhydride. A modified propylene-based random copolymer (modified polyolefin resin (1), graft amount of maleic anhydride: 1.9% by weight) was obtained by modifying the polymer with maleic anhydride.

3.0 kg of the modified polyolefin resin (1) obtained above was put into a glass-lined reaction vessel, 20 L (liter, the same applies hereinafter) of chloroform was added, and a temperature of 110 ° C. was sufficient under a pressure of 0.3 MPa. Was dissolved in. Then, 3.0 g of tert-butylperoxyisopropyl carbonate was added as a radical reaction initiator, and chlorine gas was blown in while controlling the pressure inside the kettle to 0.3 MPa to obtain a modified polyolefin resin (1) having a chlorine content of 20% by weight. Chlorinated product was obtained.

An epoxy compound was added as a stabilizer to the chlorinated product of the modified polyolefin resin (1) obtained above, chloroform was removed by a twin-screw extruder with a vent provided with a vent port for distilling off the reaction solvent under reduced pressure, and chlorine was removed. The modified polyolefin resin composition was extruded into a strand and cooled with water. Then, it was pelletized with a water-cooled pelletizer to obtain a chlorinated modified polyolefin resin (1) which is a solid substance of a chlorinated modified propylene-based random copolymer modified with maleic anhydride.

As a result of analysis of the chlorinated modified polyolefin resin (1) by gel permeation chromatography (GPC; HLC8320GPC, manufactured by Tosoh Corporation), the weight average molecular weight (Mw) was 100,000.

Next, 200 g of the chlorinated modified polyolefin resin (1) was placed in a 2 L 4-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel, and a surfactant (Liponol T / 25, manufactured by Lion). 33 g, a stabilizer (stearyl glycidyl ether) 8 g, and xylene 36 g were added, and the mixture was kneaded at 120 ° C. for 30 minutes. Next, 8 g of 2-amino-2-methyl-1-propanol was added over 5 minutes, and after holding for 5 minutes, 970 g of warm water at 90 ° C. was added over 40 minutes. After performing a reduced pressure treatment to remove a part of xylene and water, the mixture was cooled to room temperature with stirring to obtain an aqueous dispersion of the modified polyolefin resin (1). The solid content of the aqueous dispersion was 35% by weight, the pH was 7.0, the viscosity was 12 mPa · s / 25 ° C., and the average particle size was 90 nm.
The average particle size of the solid content was measured using a Zetasizer 3000HS (manufactured by Sysmex Corporation).

(Production Example 1-2: Production of an aqueous dispersion of a chlorinated modified polyolefin resin (2))
Modified polyolefin resin (2) and chlorinated modified polyolefin in the same manner as in Production Example 1 except that the amount of maleic anhydride was 0.7 parts, the amount of dicumyl peroxide was 2.1 parts, and the barrel temperature was 200 ° C. Resin (2) was obtained. The graft amount of maleic anhydride of the modified polyolefin resin (2) was 0.6% by weight, and the weight average molecular weight of the chlorinated modified polyolefin resin (2) was 120,000. The chlorinated modified polyolefin resin (2) is the same as in Production Example 1 except that the chlorinated modified polyolefin resin (2) is used and the amount of 2-amino-2-methyl-1-propanol used is 4 g. ) Was obtained. The solid content of the aqueous dispersion was 35% by weight, the pH was 7.8, the viscosity was 10 mPa · s / 25 ° C., and the average particle size was 130 nm.

(Production Example 1-3: Production of aqueous dispersion of chlorinated modified polyolefin resin (3))
A modified polyolefin resin (3) and a chlorinated modified polyolefin resin (3) were obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride was 5 parts and the amount of dicumyl peroxide was 4 parts. The graft amount of maleic anhydride of the modified polyolefin resin (3) was 3.5% by weight, and the weight average molecular weight of the chlorinated modified polyolefin resin (3) was 80,000. The chlorinated modified polyolefin resin (3) is the same as in Production Example 1 except that the chlorinated modified polyolefin resin (3) is used and the amount of 2-amino-2-methyl-1-propanol used is 15 g. ) Was obtained. The solid content of the aqueous dispersion was 35% by weight, the pH was 7.2, the viscosity was 15 mPa · s / 25 ° C., and the average particle size was 75 nm.

(Production Example 1-4: Production of aqueous dispersion of chlorinated modified polyolefin resin (4))
A modified polyolefin resin (4) and a chlorinated modified polyolefin resin (4) were obtained in the same manner as in Production Example 1 except that chlorine gas was blown so that the chlorine content was 13% by weight. The graft amount of maleic anhydride of the modified polyolefin resin (4) was 1.9% by weight, and the weight average molecular weight of the chlorinated modified polyolefin resin (4) was 96,000. The chlorinated modified polyolefin resin (4) is the same as in Production Example 1 except that the chlorinated modified polyolefin resin (4) is used and the amount of 2-amino-2-methyl-1-propanol used is 10 g. ) Was obtained. The solid content of the aqueous dispersion was 35% by weight, the pH was 7.5, the viscosity was 14 mPa · s / 25 ° C., and the average particle size was 120 nm.

(Production Example 1-5: Production of aqueous dispersion of chlorinated modified polyolefin resin (5))
A modified polyolefin resin (5) and a chlorinated modified polyolefin resin (5) were obtained in the same manner as in Production Example 1 except that chlorine gas was blown so as to have a chlorine content of 25% by weight. The graft amount of maleic anhydride of the modified polyolefin resin (5) was 1.9% by weight, and the weight average molecular weight of the chlorinated modified polyolefin resin (5) was 105,000. The chlorinated modified polyolefin resin (5) is the same as in Production Example 1 except that the chlorinated modified polyolefin resin (5) is used and the amount of 2-amino-2-methyl-1-propanol used is 10 g. ) Was obtained. The solid content of the aqueous dispersion was 35% by weight, the pH was 7.4, the viscosity was 12 mPa · s / 25 ° C., and the average particle size was 95 nm.

(Production Example 1-6: Production of aqueous dispersion of chlorinated modified polyolefin resin (6))
3 parts of maleic anhydride and dicumyl peroxide in 100 parts of a propylene-based random copolymer (about 97% propylene, about 3% ethylene, melting point: 146 ° C.) produced using a Ziegler-Natta catalyst as a polymerization catalyst. Five parts were mixed and supplied to a twin-screw extruder having L / D = 60 and φ = 40 mm using a quantitative feeder. The reaction was started with a residence time of 15 minutes and a barrel temperature of 190 ° C. (3rd to 7th barrels), and the pressure was reduced in the 9th barrel to remove unreacted maleic anhydride. A modified propylene-based random copolymer (modified polyolefin resin (6), graft amount of maleic anhydride: 1.7% by weight) was obtained by modifying the polymer with maleic anhydride.
A chlorinated modified polyolefin resin (6) was obtained in the same manner as in Production Example 1 except that the modified polyolefin resin (6) was used. The weight average molecular weight of the chlorinated modified polyolefin resin (6) was 65,000. A chlorinated-modified polyolefin resin (6) was used, and 8 g of 2-amino-2-methyl-1-propanol was changed to 15 g of morpholine in the same manner as in Production Example 1. The aqueous dispersion of 6) was obtained. The solid content of the aqueous dispersion was 35% by weight, the pH was 7.6, the viscosity was 12 mPa · s / 25 ° C., and the average particle size was 110 nm.

(Production Example 1-7: Production of aqueous dispersion of modified polyolefin resin (7))
100 parts of a propylene-based random copolymer (97% propylene component, 3 mol% ethylene component, Tm = 125 ° C.) produced using a metallocene catalyst as a polymerization catalyst, 5 parts of maleic anhydride, and 2 parts of di-t-butyl peroxide. The reaction was carried out using a twin-screw extruder set at 160 ° C. Degassing was also performed in the extruder to remove residual unreacted material. The weight average molecular weight of the obtained modified polyolefin resin (7) was 98,000, the molecular weight distribution (Mw / Mn) was 2.7, and the graft weight of maleic anhydride was 3.6% by weight.
100 g of the modified polyolefin resin (7) obtained above and 20 g of a surfactant (Emargen LS-106, manufactured by Kao Corporation) were added to a four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a dropping funnel. It was kneaded at 120 ° C. for 30 minutes.
Next, 6 g of dimethylethanolamine was added over 5 minutes, and after holding for 30 minutes, 300 g of ion-exchanged water at 90 ° C. was added over 40 minutes. Subsequently, the mixture was cooled to room temperature with stirring to obtain an aqueous dispersion of the modified polyolefin resin (7). The solid content of the aqueous dispersion was 35% by weight, pH was 7.5, the viscosity was 47 mPa · s / 25 ° C., and the average particle size was 122 nm.

(Production Example 1-8: Production of aqueous dispersion of modified polyolefin resin (8))
200 g of the modified polyolefin resin (7), 40 g of toluene, and 100 g of propylene glycol monopropyl ether obtained above were added to a four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel, and the temperature inside the flask was 90. Kneaded at ° C. for 30 minutes. Next, 12 g of dimethylethanolamine was added, and the mixture was kneaded at a flask internal temperature of 90 ° C. for 60 minutes. Then, 580 g of deionized exchanged water at 90 ° C. was added over 60 minutes. Subsequently, after removing toluene, propylene glycol monopropyl ether, and a part of water under reduced pressure, the mixture was cooled to room temperature with stirring to obtain an aqueous dispersion of the modified polyolefin resin (8). As a result of confirming the content of toluene in the modified polyolefin resin aqueous dispersion composition by gas chromatography, it was 1% by weight or less with respect to the modified polyolefin resin aqueous dispersion composition.
The solid content of the aqueous dispersion was 35% by weight, pH = 9.0, the viscosity was 15 mPa · s / 25 ° C., and the average particle size was 135 nm.

(Production Example 2-1: Cellulose Nanofiber 1)
Add 5 g (absolutely dry) of bleached unbeaten kraft pulp (whiteness 85%) derived from softwood to 500 ml of an aqueous solution of 39 mg of TEMPO (Sigma Aldrich) and 514 mg of sodium bromide, and stir until the pulp is evenly dispersed. bottom. An aqueous sodium hypochlorite solution was added to the reaction system so as to have a concentration of 5.7 mmol / g, and the oxidation reaction was started. Since the pH in the system decreased during the reaction, a 3M aqueous sodium hydroxide solution was sequentially added to adjust the pH to 10. The reaction was terminated when sodium hypochlorite was consumed and the pH in the system did not change. The mixture after the reaction was filtered through a glass filter to separate the pulp, and the pulp was thoroughly washed with water to obtain oxidized pulp (carboxylated cellulose). The pulp yield was 90%, the time required for the oxidation reaction was 90 minutes, and the amount of carboxyl groups was 1.67 mmol / g.

The oxidized pulp obtained in the above step is adjusted to 1.0% (w / v) (= 1.0% by mass) with water, and treated with an ultra-high pressure homogenizer (20 ° C., 150 MPa) 5 times. , A dispersion containing cellulose nanofiber 1 was obtained. The obtained cellulose nanofiber 1 had an average fiber length of 600 nm and an aspect ratio of 267.

The amount of carboxyl groups was measured as follows. 60 ml of a 0.5 mass% slurry (aqueous dispersion) of carboxylated cellulose was prepared, and a 0.1 M hydrochloric acid aqueous solution was added to adjust the pH to 2.5. Then, a 0.05 N aqueous sodium hydroxide solution was added dropwise, and the electrical conductivity was measured until the pH reached 11. Then, it was calculated from the amount of sodium hydroxide (a) consumed in the neutralization step of the weak acid in which the change in electrical conductivity was gradual, using the following formula.

Amount of carboxyl group [mmol / g carboxylated cellulose] = a [ml] x 0.05 / mass of carboxylated cellulose [g]

(Production Example 2-2: Cellulose Nanofiber 2)
5 g (absolutely dry) of bleached unbeaten kraft pulp (manufactured by Nippon Paper Industries, Inc., whiteness 84%) derived from coniferous trees was dissolved with 78 mg (0.5 mmol) of TEMPO (Sigma Aldrich) and 755 mg (7 mmol) of sodium bromide. The mixture was added to 500 ml of an aqueous solution and stirred until the pulp was uniformly dispersed. After adding 18 ml of an aqueous sodium hypochlorite solution (5% effective chlorine) to the reaction solution, the pH was adjusted to 10.3 with a 0.5 N hydrochloric acid aqueous solution, and the oxidation reaction was started. Since the pH of the reaction solution decreased during the reaction, a 0.5 N aqueous sodium hydroxide solution was sequentially added to adjust the pH to 10. After reacting for 2 hours, it was filtered through a glass filter and washed thoroughly with water to obtain oxidized pulp.

A 5% (w / v) aqueous dispersion of oxidized pulp was prepared, and 1% (w / v) of hydrogen peroxide was added to the dispersion to add 1% (w / v) hydrogen peroxide to the oxidized pulp, and 1M sodium hydroxide was added. The pH was adjusted to 12 with. The aqueous dispersion was heated at 80 ° C. for 2 hours to hydrolyze the oxidized pulp, filtered through a glass filter, and thoroughly washed with water.

An aqueous dispersion having a concentration of 2% (w / v) of the hydrolyzed oxidized pulp was prepared and treated 10 times with an ultra-high pressure homogenizer (treatment pressure 140 MPa) to disperse the transparent cellulose nanofibers 2. Obtained liquid. The obtained cellulose nanofiber 2 had an average fiber length of 300 nm and an aspect ratio of 92.

(Example 1)
The cellulose nanofibers 1 obtained in Production Example 2-1 were added to the aqueous dispersion of the chlorinated modified polyolefin resin (1) obtained in Production Example 1-1 in terms of solid content ratio to the chlorinated modified polyolefin resin (1). ): After adding the cellulose nanofibers 1 = 100: 0.5, stir with a TK homogenizer (manufactured by Primix Corporation) at a stirring speed of 3000 rpm for 15 minutes, and water so that the solid content concentration becomes 30%. Was added to obtain a dispersed resin composition 1. The pH of the dispersion was 8.3.

The obtained dispersed resin composition 1 was adjusted to a solid content of 1.0% by mass to obtain an aqueous suspension. Two ink droplets (manufactured by Kuretake Co., Ltd., solid content 10%) were added dropwise to 1 g of the aqueous suspension, and the mixture was stirred with a vortex mixer for 1 minute. After stirring, the dispersion was observed with an optical microscope (digital microscope KH-8700 (manufactured by Hirox)) at a magnification of 100 times, and agglomerates of 150 μm or more existing in a range of 3 mm × 2.3 mm were generated. The number ratio was evaluated.
The viscosities are the B-type viscosity (called 60 rpm, 20 ° C., B60 viscosity) and the B-type viscosity (6 rpm, 20 ° C., B6 viscosity) after allowing the obtained dispersed resin composition 1 to stand at 20 ° C. for 24 hours. The measurement was performed using a TV-10 type viscometer (manufactured by Toki Sangyo Co., Ltd.). For thixotropic properties, see T.I. I. = Evaluated from B6 viscosity / B60 viscosity.

(Examples 2 to 10, Comparative Example 1)
Dispersed resin compositions 2 to 11 were obtained in the same manner as in Example 1 except that the chlorinated modified polyolefin resin 1, cellulose nanofibers 1, and water used in Example 1 were changed to the types shown in Table 1. ..
Only in Example 2, the solid content ratio of the chlorinated modified polyolefin resin (1) and the cellulose nanofibers 2 was set to 100: 2.5.

The dispersed resin compositions obtained in Examples and Comparative Examples had a solid content of 40 parts, an aqueous acrylic resin (Bihydrol XP2427, manufactured by Sumika Bayer Urethane Co., Ltd.) had a solid content of 40 parts, and an aqueous polyurethane resin (UCOAT UWS-145, 20 parts of solid content (manufactured by Sanyo Kasei Kogyo), 20 parts of carbon ECP600JD (manufactured by Lion) of conductive carbon, and 80 parts of titanium R-960 (manufactured by DuPont) of titanium dioxide are blended according to a conventional method, and the solid content is mixed. An aqueous primer coating was prepared by diluting with ion-exchanged water so as to have a concentration of 40%.
An ultra-high rigidity polypropylene plate (trade name: TX-933A, manufactured by Mitsubishi Chemical Corporation) is coated with a primer layer using an aqueous primer paint prepared so that the film thickness is about 10 μm with an air spray gun, and then preheated. The water-based metallic color base coat paint was applied so as to have a dry film thickness of 15 μm. Then, the coated plate was preheated at 80 ° C. for 3 minutes, and an acrylic urethane solvent-based clear paint was coated on the coating film made of the base coat paint so as to have a film thickness of 30 μm. The coated plate was dried at 80 ° C. for 30 minutes and left at room temperature for 72 hours, and then a test piece having a laminated coating film was obtained, and the following adhesion evaluation and appearance evaluation were performed. The results are shown in Table 2.

[Adhesiveness]
100 grids reaching the substrate at 1 mm intervals were prepared on the coated surface, and a cellophane adhesive tape was adhered to the grids and peeled off in the 180 ° direction, and the degree to which the coating film remained was judged.

[exterior]
The coated surface was visually observed and the appearance was evaluated as follows.
◯: The appearance is uniform and good.
X: Appearance abnormalities such as unevenness and repellent are observed.

From the above results, it can be seen that by using the dispersed resin composition of the present invention, a coating treatment having a good appearance can be performed without deteriorating the adhesiveness.

Claims (10)

A dispersed resin composition containing the following components (A) to (C).
Component (A): Polyethylene using chlorine and one or more polarity-imparting agents selected from the group consisting of unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and radically polymerizable monomers. A chlorinated modified polyolefin resin obtained by modifying the resin.
Ingredient (B): Cellulose nanofibers.
Component (C): Dispersion medium. The dispersed resin composition according to claim 1, wherein the number ratio of agglomerates having an average particle size of 150 μm or more derived from the component (B) is less than 1%. The dispersed resin composition according to claim 1 or 2 , wherein the content of the component (B) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the component (A). The dispersed resin composition according to any one of claims 1 to 3 , wherein the component (C) contains water or a hydrophilic substance. The polyolefin resin is at least one polyolefin resin selected from the group consisting of a propylene homopolymer, an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer. The dispersed resin composition according to any one of claims 1 to 4, which comprises. The dispersed resin composition according to any one of claims 1 to 5 , wherein the modified weight of the component (A) due to the polarity-imparting agent is 0.1 to 30% by weight. The dispersed resin composition according to any one of claims 1 to 6 , wherein the weight average molecular weight of the component (A) is 10,000 to 500,000. A coating material containing the dispersed resin composition according to any one of claims 1 to 7. A primer coating material containing the dispersed resin composition according to any one of claims 1 to 7. A step of applying the primer coating according to claim 9 to form a wet-on primer layer, and
A method for forming a laminated coating film, which comprises a step of applying a topcoat paint on the wet-on-primer layer and drying it.