JP2017179145A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide inexpensive paint that has excellent dispersibility for a wide range of additive components and can suitably form a coating having good adhesion to a base material and a good appearance.SOLUTION: A resin composition comprises a lignin and/or a lignin derivative and further comprises a foaming agent component.SELECTED DRAWING: None

Description

The present invention relates to a resin composition, and more specifically, a resin composition that can be suitably used for various structures that require good film formability, a paint containing the resin composition, and the paint It is related with the coating film obtained.

The resin composition can form a coating film by evaporating the solvent after application and fusing the resins together. Among them, resin compositions containing emulsion polymers (emulsion compositions) using water as a solvent have recently been used in many industrial products in consideration of environmental protection, workability during coating film formation, safety for industrial products, and the like. Is used to form a coating film that exhibits various functions. For example, it is possible to obtain a vibration absorption effect and a sound absorption effect by forming a coating film for use in railway vehicles, ships, aircraft, electrical equipment, building structures, construction equipment, etc. Have been proposed (see, for example, Patent Documents 1 to 3).

By the way, lignin is a natural aromatic polymer present in trees, and is contained in a large amount in waste liquid in kraft pulp production (craft pulp waste liquid), waste liquid in sulfite pulp production (sulfite pulp waste liquid), and the like. For example, kraft lignin contained in kraft pulp waste liquor is sulfomethylated with sulfite and formaldehyde, lignin sulfonic acid or its salt contained in sulfite pulp waste liquor is partially desulfonated, limited The thing refine | purified by the external filtration process etc. is used as a dispersing agent in the field | area of dye, cement, an inorganic and organic pigment, gypsum, coal-water slurry, agrochemical, and the ceramic industry (for example, refer patent document 4).

JP 2003-193025 A JP-A-6-145454 JP-A-2-150445 JP 2011-240224 A

Various paints have been proposed as described above, but an inexpensive paint capable of suitably forming a coating film having excellent dispersibility of various additive components and excellent adhesion to a substrate and appearance. It has not been found yet.

The present invention has been made in view of the above-described present situation, and provides an inexpensive paint capable of suitably forming a coating film having excellent dispersibility of various additive components and excellent adhesion to a substrate and appearance. The purpose is to do.

The inventor paid attention to the resin composition. Next, the present inventor paid attention to lignins and / or lignin derivatives, which are plant-derived components desirable from an environmental point of view as inexpensive and easily obtainable materials, and as a result of various studies, the lignins and / or lignin derivatives were included. Furthermore, the inventors have conceived a novel resin composition containing a foaming agent component. The inventor has found that the paint obtained by using this resin composition is excellent in dispersibility of various additive components, and can suitably form a coating film having excellent adhesion to the substrate and appearance. The inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a resin composition containing lignins and / or lignin derivatives and further containing a foaming agent component.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Resin composition of the present invention>
The resin composition of the present invention contains lignins and / or lignin derivatives, and further contains a foaming agent component. Note that lignins and / or lignin derivatives are one type of resin, but as will be described later, the resin composition of the present invention further comprises a resin (more preferably an emulsion polymer) different from lignins and / or lignin derivatives. ) Is preferably included. The coating obtained by using the resin composition of the present invention is excellent in dispersibility of various additive components and can form a coating film excellent in adhesion to the substrate and appearance.
By including the lignin and / or lignin derivative and the foaming agent component, the resin composition of the present invention can provide a coating film with good appearance with suppressed swelling. The reason is estimated as follows. When the coating film is formed, the evaporation path of the volatile components inside the coating film is blocked by forming a dry film by evaporating the volatile components from the coating surface before all the volatile components are evaporated from inside the coating film. This occurs when the coating film is lifted by vapors of volatile components remaining inside the coating film. When the resin composition of the present invention contains lignins and / or lignin derivatives and a foaming agent component, foam is generated during the formation of the coating film, and the foam can be stabilized and appropriately maintained in its shape. In addition, the bubbles suitably form an evaporation path in the film on the surface of the coating film, and water drainage is maintained even when heating is continued. Thereby, a favorable coating-film external appearance is obtained.
In addition, since the coating film obtained in this way has a porous structure, when used for a damping material, it can exhibit excellent damping properties in a wide temperature range.

Lignin is one of the three major components of plant biomass such as wood (cellulose, hemicellulose, lignin) and is the most abundant on the earth as a natural aromatic polymer. Therefore, it is advantageous for preparing the resin composition of the present invention. Moreover, since the resin composition of this invention can use the lignin and its derivative which are plant-derived components and are produced in large quantities as a by-product in the paper pulp manufacturing industry, it is very desirable also in an environmental aspect.

(Lignins and / or lignin derivatives)
The lignins and / or lignin derivatives are molecules having a complicated three-dimensional network structure having a structure in which a phenylpropane skeleton that is a basic skeleton of lignin is linked.
The above lignin refers to an unmodified lignin, and may be, for example, a natural lignin present in a plant body or a lignin that has been isolated from a plant body by digestion. In addition, the lignin as isolated from the plant body by cooking may have a thioether bond, or a substituent such as a sulfonic acid group, a sulfonic acid group, or an acetyl group. In the present specification, denaturation refers to the introduction of another structural site different from the structural site possessed by the lignin to the lignin that has been isolated from the plant body by cooking.

Examples of the lignins include kraft lignin having a thioether bond in a structure in which the phenylpropane skeleton is linked, and lignin sulfonic acid (salt), and among them, the effect of the present invention is more fully exhibited. Is more preferably lignin sulfonic acid (salt). In the present specification, lignin sulfonic acid (salt) means lignin sulfonic acid and / or lignin sulfonate.
Examples of the lignin sulfonate include monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, and mixed salts thereof.
The lignins may be those obtained by further decomposing or molecular weight fractionating the lignin sulfonic acid (salt). Examples of the decomposition include hydrolysis. Examples of the molecular weight fraction include a method by ultrafiltration. Of these, hydrolysis is preferred.

As the above lignins, lignin sulfonic acid, lignin sulfonic acid sodium salt, lignin sulfonic acid magnesium salt, and lignin sulfonic acid calcium salt are preferable, and lignin sulfonic acid sodium salt, lignin from the viewpoint that the effects of the present invention can be more fully exhibited. Magnesium sulfonate and calcium lignin sulfonate are more preferable. From the viewpoint of further improving the adhesion of the coating film, magnesium lignin sulfonate is particularly preferable, and a wide range of temperatures can be used when the coating film is used for vibration damping materials. From the viewpoint of further improving the vibration damping property in the region, sodium lignin sulfonate is particularly preferable.

As the above lignins, as described above, lignin that has been isolated from the plant body by digestion can be used. More specifically, for example, kraft pulp waste liquid or sulfite pulp waste liquid can be used as it is. it can. Kraft pulp waste liquor contains kraft lignin, and sulfite pulp waste liquor contains lignin sulfonic acid. Kraft lignin and lignin sulfonic acid usually have different physical properties. Even if it is lignin, the effect of this invention can be exhibited by mix | blending in the resin composition of this invention.

In addition, lignins include waste liquid obtained by alkali cooking (alkali lignin), waste liquid obtained by acetic acid method (acetic acid lignin), waste liquid obtained by using a hydrous organic solvent as cooking liquid (organosolve lignin), water vapor It is also possible to use waste liquid (explosive lignin) obtained by the explosion method.
In addition, as said alkali cooking, the method of cooking a woody plant using alkali metal hydroxides, such as sodium hydroxide (caustic soda), is preferable.

Moreover, what adjusted suitably the solid content concentration of each waste liquid mentioned above can also be used as said lignin. The solid content concentration of the waste liquid is, for example, 10 to 70% by mass, and preferably 15 to 45% by mass.
For the preparation of the above lignins, a commonly used cooking aid can be used.

As described above, the lignin can be used as it is in the cooking liquor when obtaining pulp from plants, or can be used by appropriately adjusting the solid content concentration of the cooking liquor, but purified from the cooking liquor You may use what was done (commercial item etc.). Purification from the cooking liquor can be performed by a conventional method used for purification, such as a method of adding an acid to the cooking liquor to obtain a solution having a predetermined pH and precipitating lignins. Commercially available products of lignin sulfonate purified from cooking liquor include, for example, Pearl Rex NP (Nippon Paper, sodium lignin sulfonate), Sun Extract P321 (Nippon Paper, magnesium lignin sulfonate), Pearl Rex CP (Nippon Paper Industries Co., Ltd., calcium lignin sulfonate) or those obtained by adding an aqueous solvent to these to adjust the solid content concentration as appropriate. The preferable range of the solid content concentration is the same as the preferable solid content concentration of the waste liquid described above.

The lignin derivative refers to a lignin in which at least a part of a structure in which a phenylpropane skeleton, which is the basic skeleton of lignin is linked, is modified, and lignins such as lignin sulfonic acid (salt) are further derivatized. The derivatization corresponds to “denaturation” in the present specification, and refers to introducing another structural site different from the structural site of the lignin into the lignin that has been isolated from the plant body by cooking, For example, alkylation, amination, alkoxylation, alkoxysulfonylation, sulfoalkylation, aminoalkylation, desulfonation, and substituents such as carboxylic acid group-containing groups and (poly) alkylene glycol chain-containing groups described later are added. And so on.

The modified part in the structure of the lignin derivative is, for example, the following general formula (1);

(Wherein R ^{1 to} R ⁶ are the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group, an acyl group, an amino group, a sulfonic acid group, a sulfonic acid group, a carboxylic acid group-containing group, or a (poly) alkylene glycol chain. A containing group, a hydrocarbon group, or a direct bond or thioether bond with another phenylpropane skeleton, and at least one of R ^{1 to} R ⁶ represents a direct bond or thioether bond with another phenylpropane skeleton. And at least one of R ^{1 to} R ⁶ represents a structure represented by an alkoxy group, a carboxylic acid group-containing group, a (poly) alkylene glycol chain-containing group, or a hydrocarbon group. .

The (poly) alkylene glycol chain-containing group may be a group having only a (poly) alkylene glycol chain or a group having a (poly) alkylene glycol chain and other structural sites. Examples of other structural sites include hydrocarbon groups such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The (poly) alkylene glycol chain-containing group is preferably a group having only a (poly) alkylene glycol chain, or a group in which a (poly) alkylene glycol chain is added to an aromatic ring having an alkylene group having 1 to 30 carbon atoms. .
The terminal structure of the (poly) alkylene glycol chain is not particularly limited, and may have a substituent. It is preferable that a hydrogen atom or a hydrocarbon group is bonded to the terminal oxygen atom. As said hydrocarbon group, a C1-C2 alkyl group is preferable.

As the (poly) alkylene glycol chain, the oxyalkylene group having 2 to 4 carbon atoms such as oxyethylene group, oxypropylene group and oxybutylene group is 50 to 100 mol% based on the total number of oxyalkylene groups. Preferably. More preferably, an oxyethylene group occupies 50-100 mol% with respect to the total number of oxyalkylene groups.

It is preferable that the average added mole number of the alkylene oxide which comprises the said (poly) alkylene glycol chain is 3-200. The average number of moles of alkylene oxide added means the average value of the number of moles of alkylene oxide added in one polyalkylene glycol chain in the lignin.

As said alkoxy group, it is preferable that it is a C1-C15 alkoxy group, More preferably, it is a C1-C2 alkoxy group.
The carboxylic acid group-containing group is not particularly limited as long as it has a carboxylic acid group (—COOH) or a salt thereof, and even a carboxylic acid group or a salt thereof alone may be a carboxylic acid group or a salt thereof and other structures. It may be a group having a site. Examples of other structural sites include hydrocarbon groups such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The carboxylic acid group-containing group includes a carboxylic acid group or a salt thereof, an aliphatic hydrocarbon group having 1 to 30 carbon atoms to which the carboxylic acid group or salt thereof is bonded, or a carbon number to which an aromatic carboxylic acid group is bonded 1-20 alkylene groups are preferred. The aromatic carboxylic acid group is an aromatic group having a carboxylic acid group or a salt thereof.
As said hydrocarbon group, a C1-C30 hydrocarbon group is preferable, More preferably, it is a 1-5 hydrocarbon group.
^One of the substituents other than the hydrogen atoms of R ^{1 to} R ⁶ may be bonded to the benzene ring of the lignin skeleton, or may be bonded to two or more.

The lignins and / or lignin derivatives preferably have a weight average molecular weight of 100 to 40,000. When the lignin and / or lignin derivative has such a weight average molecular weight, the function of the obtained vibration damping material can be more fully exhibited. The weight average molecular weight is more preferably 500 to 30000, and still more preferably 2000 to 15000. The weight average molecular weight of the lignins and / or lignin derivatives can be measured using GPC under the conditions described in the examples described later.

The raw materials for the lignins and / or lignin derivatives are not particularly limited, and any of natural products and synthetic products can be used. When natural products are used, the type of wood used as a raw material is not particularly limited, and either wood-based materials obtained from woody plants or herbaceous materials obtained from herbaceous plants should be used. Can do. Examples of woody plants include conifers such as cedar, fir, hinoki and pine, and broad-leaved trees such as eucalyptus, acacia, birch, beech and oak. Herbaceous plants include rice straw, cereals, bagasse, bamboo, kenaf, straw and the like.
The lignins and / or lignin derivatives are preferably woody products obtained from woody plants as raw materials, and more preferably those obtained from softwoods as raw materials.

(Method for producing lignins and / or lignin derivatives)
The lignins can be obtained using a conventionally known method.
The method for modifying the lignin with a substituent or the like for obtaining the lignin derivative is not particularly limited. For example, it can be performed by reacting a reactive group such as a hydroxyl group of the lignin with a compound having a substituent.
When the substituent is a (poly) alkylene glycol chain-containing group, (1) reacting an alkylene oxide such as ethylene oxide or a compound having a (poly) alkylene glycol chain with a hydroxyl group of lignin, or ( 2) It can be modified by reacting a compound having a (poly) alkylene glycol chain with an aldehyde compound and then adding lignin and reacting it.
The reaction (1) above produces a modified lignin in which the phenolic hydroxyl group of the lignin and the compound having a (poly) alkylene oxide or (poly) alkylene glycol chain are directly bonded, and the reaction (2) above produces a lignin. A modified lignin is produced in which a benzene ring of a kind and a compound having a (poly) alkylene glycol chain are bonded via a divalent linking group.

Examples of the compound having a (poly) alkylene glycol chain in the reaction (1) include polyalkylene glycol compounds such as polyethylene glycol and polypropylene glycol; polyethylene glycol-monoethyl-glycidyl ether, polyethylene glycol-monomethyl-glycidyl ether, lauryl alcohol -Monofunctional glycidyl ether compounds such as polyethylene oxide-glycidyl ether; bifunctional glycidyl ether compounds such as poly (ethylene glycol) diglycidyl ether and poly (propylene glycol) diglycidyl ether; , Also referred to as an epoxy group.) Was reacted with an alkoxide compound such as methoxy or ethoxy to reduce the functionality of the glycidyl ether group. Glycidyl ether compound; monofunctional epoxy polyalkylene glycol compound obtained by the reaction of alkoxy polyalkylene glycol and epichlorohydrin epihalohydrin phosphorus such as methoxy polyethylene glycol; methoxy polyethylene glycol acrylate.
Examples of the compound having a (poly) alkylene glycol chain in the reaction (2) above include aromatic (poly) alkylene glycol compounds such as an ethylene oxide adduct of phenol.

When the substituent is a carboxylic acid group-containing group, for example, after reacting a compound having a carboxylic acid group with an aldehyde compound, lignin can be added and reacted to cause modification.
By this reaction, a modified lignin in which the benzene ring of lignin and the compound having a carboxylic acid group are bonded via a divalent linking group is generated.
Examples of the compound having a carboxylic acid group include aromatic carboxylic acid compounds such as 2-hydroxyphenylacetic acid.

The content of the lignin and / or lignin derivative is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass in 100% by mass of the solid content of the resin composition of the present invention. % Or more, more preferably 7% by mass or more, and most preferably 9% by mass or more. The content is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
In addition, solid content here means components other than solvents, such as an aqueous solvent.

(Foaming agent component)
The resin composition of the present invention further contains a foaming agent component. The said foaming agent component means all the agents which have foaming properties, such as heat foaming property and mechanical foaming property, and can function as a foaming agent regardless of the purpose of use. That is, the foaming agent component in the resin composition may have other functions as long as it can function as a foaming agent. Examples of the purpose of use include the purpose of use as a dispersant, a wet penetrant, a surfactant and the like.

As said foaming agent component, 1 type (s) or 2 or more types of a surfactant component, a heat expansion capsule type | mold foaming agent, and another foaming agent can be used. The surfactant component can be used, for example, as a mechanical foaming agent for mechanical foaming by stirring or the like.
In addition, the foaming agent component (for example, surfactant component) may be a compound or a constituent unit constituting a part of the emulsion polymer described later, but is preferably a compound.
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a polymer surfactant, and one or more of these are used. be able to.
Examples of the anionic surfactant include fatty acid (salt), alkyl ether carboxylic acid (salt), N-acyl amino acid (salt), alkane sulfonic acid (salt), α-olefin sulfonic acid (salt), α-sulfo. Alkyl ester (salt), alkyl sulfosuccinic acid (salt), acyl isethionic acid (salt), N-acyl-N-alkyl taurine (salt), alkyl sulfate (salt), alkyl ether sulfate (salt), alkyl phosphate (Salts), polyoxyalkylene alkyl ether phosphates (salts), alkyl diphenyl ether disulfonic acids (salts) and the like are preferred, and one or more of these can be used.

As said anionic surfactant, 1 type (s) or 2 or more types of reactive surfactants, such as a sulfosuccinate type reactive anionic surfactant and an alkenyl succinate type reactive anionic surfactant, should be used. Can do.
Commercially available sulfosuccinate-type reactive anionic surfactants include Latemul S-120, S-120A, S-180 and S-180A (all trade names, manufactured by Kao Corporation), Eleminol JS-20 (Product) Name, manufactured by Sanyo Chemical Industries).
As a commercial item of an alkenyl succinate type reactive anionic surfactant, Latemul ASK (trade name, manufactured by Kao Corporation) and the like can be mentioned.
Further, alkylbenzene sulfonic acid (salt), polyoxyethylene polycyclic phenyl ether sulfate (salt), polyoxyalkylene alkyl ether sulfate (salt), and the like can be used as the anionic surfactant.

The nonionic surfactant is not particularly limited. For example, polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan aliphatic ester; polyoxyethylene sorbitan aliphatic ester; aliphatic such as monolaurate of glycerol Monoglyceride; polyoxyethyleneoxypropylene copolymer; condensation products of ethylene oxide and aliphatic amines, amides or acids. For example, as a commercial product, Emulgen 1118S (manufactured by Kao Corporation) and the like can be mentioned. Also, allyloxymethylalkoxyethylhydroxypolyoxyethylene (for example, “ADEKA rear soap ER-20” manufactured by ADEKA), polyoxyalkylene alkenyl ether (for example, “Latemul PD-420”, “Latemul PD-” manufactured by Kao Corporation) Nonionic surfactants having reactivity such as “430” and the like can also be used. These 1 type (s) or 2 or more types can be used.

The cationic surfactant is not particularly limited, and examples thereof include dialkyldimethylammonium salts, ester-type dialkylammonium salts, amide-type dialkylammonium salts, dialkylimidazolinium salts, and the like. Can be used.

The amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropylbetaine, alkylhydroxysulfobetaine, and the like. 1 type (s) or 2 or more types can be used.

The polymer surfactant is not particularly limited. For example, polyvinyl alcohol and a modified product thereof; (meth) acrylic water-soluble polymer; hydroxyethyl (meth) acrylic water-soluble polymer; hydroxypropyl (meth) acrylic Water-soluble polymers such as polyvinyl pyrrolidone, and one or more of them can be used.

The surfactant may further have a substituent. Examples of the substituent include a hydrocarbon group, amino group, alkoxy group, alkylamino group, alkoxysulfonyl group, sulfoalkyl group, aminoalkyl group, carboxylic acid group, polyalkylene oxide chain-containing group, and alkenyloxy group. It is done.

The surfactant component in the resin composition of the present invention may be a compound. When the resin composition of the present invention contains a polymer such as an emulsion polymer described later, it is a structural unit constituting a part of the polymer. May be. For example, a polymer in which a part of the structural unit is a component derived from a surfactant can be prepared by performing polymerization by adding at least a part of the reactive surfactant described above to the raw material monomer component of the polymer. The reactive surfactant is usually a surfactant having a reactive carbon-carbon unsaturated bond. However, the surfactant component is preferably a compound having no reactive carbon-carbon unsaturated bond from the viewpoint of improving the appearance of the coating film. When a compound having no reactive carbon-carbon unsaturated bond is used as the surfactant component, the resin composition of the present invention contains a compound different from the emulsion polymer, in addition to the constituent unit of the emulsion polymer. It will be. Thereby, the effect of this invention which makes a coating-film external appearance favorable can be exhibited more notably.

As said heat expansion capsule type | mold foaming agent, commercial items, such as brand name F-30 (made by Matsumoto Yushi Co., Ltd.), are mentioned.

The foaming agent component is preferably a surfactant component and / or a heat-expandable capsule-type foaming agent, more preferably a surfactant component, from the standpoint of exhibiting the effects of the present invention more remarkably. .

The blowing agent component can be obtained by appropriately using a conventionally known method. Moreover, it is also possible to use a commercially available product as a foaming agent component or a product obtained by adding an aqueous solvent to a commercially available product and appropriately adjusting the solid content concentration.

The content of the foaming agent component in the resin composition of the present invention is preferably 0.1% by mass or more with respect to 100% by mass of the lignins and / or lignin derivatives. The content of the blowing agent component is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, from the viewpoint of more prominently exerting the effects of the present invention. % Or more is particularly preferable. Further, the content of the foaming agent component is preferably 300% by mass or less, more preferably 200% by mass or less, still more preferably 100% by mass or less, and 50% by mass or less. Is more preferable, and 20% by mass or less is particularly preferable.

The content of the foaming agent component in the resin composition of the present invention described above can be calculated including the constituent units of the emulsion polymer by summing up the amounts of all foaming agents used as raw materials. . The content can also be calculated by summing the amount of the foaming agent (compound) in the resin composition of the present invention and the amount of the structural unit derived from the foaming agent in the emulsion polymer.
Moreover, it is also one of the preferable forms in the resin composition of this invention that the preferable content of the foaming agent (compound) in the resin composition of this invention exists in the range of the preferable content of the foaming agent component mentioned above. It is. In this preferred embodiment, in the resin composition of the present invention, a foaming agent component may be included as a constituent unit of the emulsion polymer in addition to the foaming agent.
Content of the foaming agent in the resin composition of this invention can be calculated | required by analyzing the component extracted from the coating film after drying with a high performance liquid chromatograph. Even when a foaming agent having a reactive carbon-carbon unsaturated bond at the time of polymerization is used, it is possible to analyze what is not a constituent unit of the emulsion polymer.

(Emulsion polymer)
The resin composition of the present invention preferably further contains an emulsion polymer. The emulsion polymer is preferably obtained by emulsion polymerization of monomer components. However, the emulsion polymer is obtained by adding a surfactant to a polymer obtained by polymerization other than emulsion polymerization such as suspension polymerization. There may be. In addition, in this specification, an emulsion polymer means the polymer which forms emulsion particle | grains in a resin composition.

When the resin composition of the present invention contains an emulsion polymer, the emulsion polymer may be an emulsion polymer obtained by emulsion polymerization using a monomer emulsion containing all of the above-described surfactant components and monomer components as raw materials. Obtained by emulsion polymerization using a monomer emulsion containing a part of a surfactant component and a monomer component as a raw material to obtain an emulsion polymer, and then adding the remainder of the surfactant component to the obtained emulsion polymer. May be used. Thus, by emulsion polymerization using a monomer emulsion containing at least a part of a surfactant component and a monomer component as a raw material, at least a part of the surfactant component is included as a surfactant component that forms emulsion particles. It may be. That is, when the surfactant component usually has a hydrophilic group (for example, an acid (salt) group) and a hydrophobic group (for example, a hydrocarbon group), the component covers the surface of the emulsion particles. The hydrophilic group may face the solvent side such as an aqueous solvent (opposite side of the emulsion particles), and the hydrophobic group of the component may face the emulsion particle side. Here, the fact that the component covers the surface of the emulsion particles may not completely cover, for example, the emulsion particles may be exposed in some places.

The emulsion polymer according to the present invention preferably has a weight average molecular weight of 30,000 to 500,000. When the emulsion polymer according to the present invention has such a weight average molecular weight, the appearance of the obtained coating film is more excellent, and when the coating film is used as a vibration damping material, it exhibits better vibration damping properties. it can. The weight average molecular weight of the emulsion polymer according to the present invention is more preferably 35,000 or more, further preferably 50,000 or more, and particularly preferably 90,000 or more. The weight average molecular weight is more preferably 420,000 or less, still more preferably 400,000 or less, and particularly preferably 270,000 or less.
In addition, the weight average molecular weight (Mw) of an emulsion polymer can be measured on the conditions as described in the Example mentioned later using GPC.

The emulsion polymer according to the present invention preferably has a glass transition temperature of -20 to 40 ° C. When using an emulsion polymer having such a glass transition temperature as the emulsion polymer according to the present invention, the appearance of the resulting coating film is more excellent, and when the coating film is used as a vibration damping material, the practical temperature of the coating film It is possible to effectively exhibit the vibration damping property in the region. The glass transition temperature of the emulsion polymer according to the present invention is more preferably −15 to 35 ° C., and further preferably −10 to 30 ° C.
The glass transition temperature (Tg) can be calculated by the method described in Examples described later. Further, when at least one of the emulsion polymers according to the present invention is obtained by multistage polymerization (for example, in the case of emulsion particles having a core part and a shell part described later), the glass transition temperature is It means Tg (total Tg) calculated from the monomer composition used in all stages.

When at least one of the emulsion polymers according to the present invention is in a form in which two or more polymer chains are complexed, the glass transition temperature of one polymer chain (for example, the polymer chain of the core portion) is 0 to 60 ° C. Preferably there is. More preferably, it is 10-50 degreeC.
Moreover, it is preferable that the glass transition temperature of the other polymer chain (for example, polymer chain of a shell part) is -30-30 degreeC. More preferably, it is -20-20 degreeC.
Moreover, it is preferable that the difference of the glass transition temperature of one polymer chain and the other polymer chain is 5-60 degreeC. By providing a difference in the glass transition temperature in this manner, for example, when applied to a damping material application, it becomes possible to express a higher damping property under a wide temperature range, and is particularly in a practical range of 20 to Damping performance in the 60 ° C. region is further improved. The difference in glass transition temperature is more preferably 10 to 50 ° C, still more preferably 20 to 40 ° C.

The emulsion polymer preferably has an SP value of 6 or more, more preferably 7 or more, and preferably 8 or more from the standpoint of affinity with a solvent and its influence on film formation. Further preferred. The SP value is preferably 12 or less, more preferably 11 or less, still more preferably 10 or less, and particularly preferably 9 or less.

The calculation method of the SP value in the emulsion polymer is made by Fedors (Polymer Eng. Sci., 14, No. 2, 147, 1974) and Tortorello et al. (J. Coat. Technol., 55, 696, 99, 1983). Method.

In the formula, δ is the SP value of the polymer. Δe ₁ is a calculated value (kcal / mol) of the evaporation energy of each monomer component constituting the polymer, and ΣΔe ₁ is a total value of the calculated values of all the monomer components constituting the polymer. ΔV _m is a calculated value (ml / mol) of each monomer component constituting the polymer, and ΣΔV _m is a sum of the calculated values of all monomer components constituting the polymer. x is the molar distribution of each monomer component constituting the polymer.
In addition, the calculation value used normally can be used for the evaporation energy of a monomer component, and the molecular volume of a monomer component.
Thus, the SP value of the emulsion polymer can be adjusted by adjusting the type of monomer to be constituted and the component ratio thereof.

The emulsion polymer preferably includes, for example, at least one polymer selected from the group consisting of (meth) acrylic polymers, diene polymers, and vinyl acetate polymers.

The said (meth) acrylic-type polymer means the polymer which has a structural unit derived from a (meth) acrylic-type monomer. The (meth) acrylic monomer refers to a monomer having an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or atomic group, or a derivative of such a monomer.

The (meth) acrylic polymer is preferably a (meth) acrylic acid polymer. The (meth) acrylic acid polymer refers to a polymer having a structural unit derived from a (meth) acrylic acid monomer, and the (meth) acrylic acid monomer refers to an acryloyl group or a methacryloyl group, or hydrogen in these groups. An atom has a group replaced with another atom or atomic group, and a carboxylic acid group (—COOH group), a carboxylic acid group (—COOM group), or an acid anhydride group (—C (═O)) -O-C (= O) -group). M represents a metal salt, an ammonium salt, or an organic amine salt. Examples of the metal atom forming the metal salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as calcium and magnesium; trivalent metals such as aluminum and iron. Atoms are preferred. As the organic amine forming the organic amine salt, alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. The (meth) acrylic acid monomer is preferably (meth) acrylic acid (salt). (Meth) acrylic acid (salt) is a monomer having an acryloyl group or a methacryloyl group and having a carboxylic acid group (—COOH group) or a carboxylic acid group (—COOM group).

The (meth) acrylic acid polymer may be composed only of a structural unit derived from a (meth) acrylic acid monomer, but a structural unit derived from a (meth) acrylic acid monomer, and other It is preferable that it comprises a structural unit derived from a copolymerizable unsaturated monomer. That is, it is preferable that the monomer component for obtaining the (meth) acrylic acid-based polymer comprises a (meth) acrylic acid-based monomer and other copolymerizable unsaturated monomers, The content ratio of the (meth) acrylic acid monomer described later and the content ratio of other copolymerizable unsaturated monomers are more preferable. By including the (meth) acrylic acid monomer, the dispersibility of pigments and other additives is improved in the coating material including the resin composition of the present invention, and the function of the resulting coating film is improved. . Moreover, it becomes easy to adjust a glass transition temperature, the acid value of a polymer, other physical properties, etc. by containing the copolymerizable unsaturated monomer.

The monomer component for obtaining the (meth) acrylic acid polymer is 0.1 to 5% by mass of the (meth) acrylic acid monomer with respect to 100% by mass of all monomer components used as the raw material of the emulsion polymer, and It is preferable to contain 95 to 99.9% by mass of other copolymerizable unsaturated monomers. The monomer component is more preferably a (meth) acrylic acid monomer of 0.3% by mass or more, and other copolymerizable unsaturated monomers of 99.7% by mass or less, and a (meth) acrylic acid monomer. Is more preferably 0.5% by mass or more, and other copolymerizable unsaturated monomer is 99.5% by mass or less, (meth) acrylic acid monomer is 0.7% by mass or more, and other copolymers It is particularly preferred that the possible unsaturated monomers are 99.3% by weight or less. The monomer component is preferably 5% by mass or less of (meth) acrylic acid monomer, 95% by mass or more of other copolymerizable unsaturated monomer, and 4% by mass of (meth) acrylic acid monomer. %, More preferably 96% by mass of other copolymerizable unsaturated monomers, 3% by mass or less of (meth) acrylic acid monomer, 97% by mass of other copolymerizable unsaturated monomers It is still more preferable that it is above. By setting it within such a range, the monomer component is stably copolymerized.

In the present specification, the total monomer component used as the raw material of the emulsion polymer is derived from the monomer unit constituting the emulsion polymer in the resin composition of the present invention, and the monomer used as the raw material of the emulsion polymer. Refers to oligomers and monomers but does not refer to blowing agent components. The content of the component is the total amount of the foaming agent (a compound different from the emulsion polymer) and the structural unit derived from the compound in the emulsion polymer. In other words, the content of the component is the total amount of all the foaming agents used in obtaining the resin composition of the present invention.

Other copolymerizable unsaturated monomers include (meth) acrylic monomers other than (meth) acrylic acid monomers; unsaturated monomers having an aromatic ring; acrylonitrile; polyfunctional unsaturated compounds such as trimethylolpropane diallyl ether And monomers.
As the (meth) acrylic monomer other than the (meth) acrylic acid monomer, for example, an acryloyl group or a methacryloyl group, or a group in which a hydrogen atom in these groups is replaced with another atom or atomic group, In addition, a monomer having a carboxylic acid ester group or a derivative of such a monomer can be mentioned.

Examples of the (meth) acrylic monomer having a carboxylate group include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate , Isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl methacrylate, isooctyl methacrylate Acrylate, isooctyl methacrylate, nonyl acrylate, nonyl methacrylate, isononyl acrylate, isononyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl Acrylate, octadecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diallyl phthalate, triallyl cyanurate, ethylene glycol dia Kure Ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate , Allyl acrylate, allyl methacrylate, etc .; esterified products of (meth) acrylic acid monomers other than these, and the like, and it is preferable to use one or more of these.

As a monomer component used as a raw material for the (meth) acrylic acid polymer, a (meth) acrylic monomer other than the (meth) acrylic acid monomer is added to 100% by mass of all monomer components used as a raw material for the emulsion polymer. On the other hand, the content is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more. Moreover, it is preferable to contain 99.9 mass% or less of (meth) acrylic-type monomers other than the said (meth) acrylic acid-type monomer with respect to 100 mass% of all the monomer components. It is more preferable.

Examples of the unsaturated monomer having an aromatic ring include divinylbenzene, styrene, α-methylstyrene, vinyltoluene, and ethylvinylbenzene.

The diene polymer in the resin composition of the present invention is obtained by polymerizing a monomer component containing a diene monomer. The diene monomer may be a monomer having two double bonds, but the double bond is preferably one separated by one single bond.
Moreover, as a diene monomer, a C4-C18 thing is preferable, a C4-C12 thing is more preferable, a C4-C8 thing is still more preferable, and a butadiene is especially preferable.

The diene polymer is obtained, for example, by copolymerizing a monomer component composed of 5 to 70% by mass of a diene monomer and 30 to 95% by mass of another copolymerizable unsaturated monomer. Is preferred.

The other copolymerizable unsaturated monomer used as the raw material for the diene polymer is not particularly limited, but is a (meth) acrylic monomer other than the (meth) acrylic acid monomer described above, or an unsaturated ring having an aromatic ring. Examples thereof include monomers and other copolymerizable unsaturated monomers. Preferred types are the same as those described above. For example, methyl methacrylate is preferable as the (meth) acrylic monomer other than the (meth) acrylic acid monomer described above. Moreover, styrene is preferable as the unsaturated monomer having an aromatic ring. Furthermore, as other copolymerizable unsaturated monomer, acrylonitrile is preferable. Suitable examples of the diene polymer include acrylonitrile butadiene rubber (NBR), methyl methacrylate butadiene rubber (MBR), styrene butadiene rubber (SBR), and the like, and one or more of these may be used. it can.
In the present specification, the polymer in the resin composition of the present invention has at least one structure derived from a (meth) acrylic monomer even if it has at least one structure derived from a diene monomer in the structure. Those having a (meth) acrylic polymer and those having no structure derived from a (meth) acrylic monomer are diene polymers.

The vinyl acetate polymer in the resin composition of the present invention is obtained by polymerizing a monomer component containing vinyl acetate. The vinyl acetate polymer is preferably obtained by polymerizing a monomer component having a vinyl acetate content of 50% by mass or more. In addition, although it does not restrict | limit especially as components other than vinyl acetate in the monomer component used as the raw material of a vinyl acetate type polymer, (meth) acrylic monomers other than the (meth) acrylic acid type monomer mentioned above, unsaturated having an aromatic ring Examples thereof include monomers and other copolymerizable unsaturated monomers.
In the present specification, the polymer in the resin composition of the present invention has at least one structure derived from a (meth) acrylic monomer even if the polymer has at least one structure derived from vinyl acetate. For those having a (meth) acrylic polymer, having no structure derived from a (meth) acrylic monomer and having at least one structure derived from a diene monomer, a diene polymer and a (meth) acrylic polymer Those having neither a monomer-derived structure nor a diene-based monomer-derived structure are regarded as vinyl acetate polymers.

The resin composition of the present invention may contain one type of emulsion polymer obtained by polymerizing monomer components, or may contain two or more types. When the resin composition of the present invention contains two or more types of emulsion polymers, it may be a mixture obtained by mixing (blending) two or more types of emulsion polymers. It may be an emulsion polymer in which two or more polymer chains obtained by producing a polymer chain-containing product (for example, multistage polymerization) is combined. When mixing two or more emulsion polymers, at least one of the two or more emulsion polymers is at least one selected from the group consisting of a (meth) acrylic polymer, a diene polymer, and a vinyl acetate polymer. It is preferable. Moreover, what is necessary is just to set manufacturing conditions, such as monomer dripping conditions suitably, in order to manufacture what contains 2 or more types of polymer chains in a series of manufacturing processes. Examples of the composite of two or more polymer chains include a form having a core part and a shell part. The emulsion polymer according to the present invention has a core part and a shell part. For example, the emulsion polymer according to the present invention comprises two kinds of emulsion polymers, one of the two kinds of emulsion polymers being the core part and the other. Forming a shell part. Note that the emulsion polymer is at least one selected from the group consisting of a (meth) acrylic polymer, a diene polymer, and a vinyl acetate polymer, for example, a (meth) acrylic monomer, a diene monomer, And at least 1 sort (s) of monomer selected from the group which consists of vinyl acetate should just be contained in the monomer component which forms the core part of an emulsion, and the monomer component which forms a shell part.

Further, for example, at least one of two or more emulsion polymers forming the emulsion particles may be in a form in which two or more polymer chains are combined.

When the emulsion polymer is in a form in which two or more kinds of polymer chains are combined, one polymer chain and the other polymer chain may be completely compatible with each other and may have a homogeneous structure in which they cannot be distinguished. , They may not be completely compatible but may be formed inhomogeneously (for example, a core-shell composite structure or a microdomain structure). In order to draw out and produce a stable emulsion, for example, a core-shell composite structure is preferable.
An emulsion polymer having a core-shell composite structure can exhibit excellent vibration damping properties over a wide range from room temperature to high temperature when used for vibration damping materials, for example. In the core / shell composite structure, the surface of the core part is preferably covered with the shell part. In this case, it is preferable that the surface of the core part is completely covered with the shell part, but it may not be completely covered. For example, the core part may be covered in a mesh shape or in some places. The part may be exposed.

The average particle size of the emulsion particles composed of the emulsion polymer is preferably 80 to 450 nm.
By using emulsion particles having the above average particle diameter in this range, basic performance such as coating film appearance and coatability can be made sufficient. The average particle diameter of the emulsion particles is more preferably 400 nm or less, still more preferably 350 nm or less. The average particle size is preferably 100 nm or more.
The average particle diameter of the emulsion particles can be measured by the method described in Examples described later.

The solid content of the emulsion polymer is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, in 100% by mass of the solid content of the resin composition of the present invention. It is more preferable that it is 50 mass% or more. The content is preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 95% by mass or less, and particularly preferably 93% by mass or less. Most preferably, it is 91 mass% or less.
In addition, solid content means components other than solvents, such as an aqueous solvent.

Although the manufacturing method of the said emulsion polymer is not restrict | limited in particular, For example, it can manufacture by the method similar to the manufacturing method of the emulsion for damping materials of Unexamined-Japanese-Patent No. 2011-231184. The emulsion polymer is preferably produced by emulsion polymerization, but a method other than emulsion polymerization, for example, a method of forming an emulsion by acting a surfactant on a polymer polymerized by suspension polymerization is used. May be.

The resin composition of the present invention contains lignins and / or lignin derivatives, a foaming agent component, and the above-described emulsion polymer as necessary, but may contain other components.
When the resin composition of the present invention contains other components, the proportion of the other components in the mass of the resin composition of the present invention is not particularly limited, but is preferably, for example, 10% by mass or less. More preferably, it is 5 mass% or less. The term “other components” as used herein means the non-volatile content (solid content) remaining in the coating film even after the resin composition of the present invention is applied and dried by heating. Volatile components such as aqueous solvents are Not included. Examples of other components include oligomers and monomers derived from monomers used as raw materials for emulsion polymers, and components similar to those derived from various additives contained in the paint of the present invention described later.

The resin composition of the present invention preferably contains a solvent.
The content of the solvent is preferably 3% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more, in 100% by mass of the resin composition of the present invention. It is particularly preferably 30% by mass or more. The content of the solvent is preferably 97% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and further preferably 60% by mass or less. It is preferably 50% by mass or less.

The solvent is preferably an aqueous solvent. In this specification, the aqueous solvent may contain other organic solvents as long as it contains water, but is preferably water. For example, when the resin composition of the present invention contains an emulsion polymer, the emulsion polymer is preferably dispersed in an aqueous solvent. In this specification, being dispersed in an aqueous solvent means being dispersed without being dissolved in an aqueous solvent.

Although it does not specifically limit as pH of the resin composition of this invention, It is preferable that it is 2-10, It is more preferable that it is 3-9.5, It is still more preferable that it is 7-9. The pH of the resin composition of the present invention can be adjusted by adding ammonia water, water-soluble amines, alkaline hydroxide aqueous solution, and the like to the emulsion polymer.
In this specification, pH can be measured by the method as described in the Example mentioned later.

Although it does not specifically limit as the viscosity of the resin composition of this invention, It is preferable that it is 1-10000 mPa * s, It is more preferable that it is 5-4000 mPa * s, It is still more preferable that it is 10-2000 mPa * s. More preferably, it is 30-1000 mPa * s, and it is especially preferable that it is 80-500 mPa * s.
In the present specification, the viscosity can be measured according to the conditions described in Examples described later.

The resin composition of the present invention can be used by itself to form a vibration-damping coating, but is usually used to obtain the paint of the present invention described later.

The resin composition of the present invention may be heat foamable or mechanical foamable, but is preferably heat foamable. Moreover, it is preferable that the resin composition of this invention is an object for heat drying. In the present specification, the term “for heat drying” refers to heat drying when forming a coating film. In the present specification, “resin composition” can be rephrased as “heat-foamable resin composition” or “heat-drying resin composition”. The present invention may be, for example, a heat-foamable resin composition containing lignins and / or lignin derivatives and further containing a foaming agent component. The present invention may also be a heat-drying resin composition containing lignins and / or lignin derivatives and further containing a foaming agent component.

The resin composition of the present invention is preferably used for a vibration damping material, for example. The vibration damping material is preferably an automobile vibration damping material. In the present specification, “resin composition” can be restated as “damping material”. The present invention may be, for example, a vibration damping material that includes lignins and / or lignin derivatives and further includes a foaming agent component.

<Coating material of the present invention>
The present invention is also a paint comprising the resin composition of the present invention and a pigment.
In the solid content of 100% by mass of the coating material of the present invention, the solid content of the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. preferable. The solid content of the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

As the pigment, for example, one or more of an inorganic colorant, an organic colorant, a rust preventive pigment, a filler and the like can be used. Examples of the inorganic colorant include titanium oxide, carbon black, and a petiole. Examples of the organic colorant include dyes and natural pigments. Examples of the rust preventive pigment include a metal phosphate, a metal molybdate, and a metal borate. As fillers, inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, glass talk, magnesium carbonate, aluminum hydroxide, diatomaceous earth, clay; scaly inorganic substances such as glass flakes and mica Fillers; Examples thereof include fibrous inorganic fillers such as metal oxide whiskers, glass fibers, and wollastonite. Above all, the pigment is preferably a filler, and more preferably an inorganic filler.
The pigment preferably has an average particle diameter of 1 to 50 μm. The average particle diameter of the pigment can be measured by a laser diffraction particle size distribution measuring device, and is a value of 50% diameter by weight from the particle size distribution.
As a compounding quantity of the said pigment, it is preferable to set it as 10-900 mass parts with respect to 100 mass parts of solid content of resin in the coating material of this invention, More preferably, it is 200-800 mass parts, More preferably, it is 300. It is -500 mass parts.

The paint of the present invention may further contain a dispersant.
Examples of the dispersant include inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and organic dispersants such as polycarboxylic acid-based dispersants.
As a compounding quantity of the said dispersing agent, 0.1-8 mass parts is preferable at solid content with respect to 100 mass parts of solid content of resin in the coating material of this invention, 0.5-6 mass parts is more preferable, 1 -3 mass parts is still more preferable.

The paint of the present invention may further contain a thickener.
Examples of the thickener include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like.
As a compounding quantity of the said thickener, 0.01-5 mass parts is preferable by solid content with respect to 100 mass parts of solid content of the resin in the coating material of this invention, 0.1-4 mass parts is more preferable, 0.3-2 mass parts is still more preferable.

The paint of the present invention may further contain other components. Other components include, for example, a solvent; a gelling agent; an antifoaming agent; a plasticizer; a stabilizer; a wetting agent; an antiseptic; an antifoaming agent; an antiaging agent; These can be used, and one or more of these can be used.
The pigment, dispersant, thickener, and other components are, for example, a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver, etc., and a polymer emulsion or a foaming agent according to the present invention. Can be mixed.

Examples of the solvent include water; and organic solvents such as ethylene glycol, butyl cellosolve, butyl carbitol, and butyl carbitol acetate. What is necessary is just to set suitably as a compounding quantity of a solvent, in order to adjust solid content concentration of the coating material of this invention.

A wet film thickness of 6 mm is applied on a 0.8 mm * 70 mm * 150 mm steel plate (ED steel plate) obtained by electrodeposition-coating the paint of the present invention using a cationic electrodeposition paint Electron “KG-400” manufactured by Kansai Paint Co., Ltd. Apply and immediately baked at 120 ° C for 30 minutes with the coating surface vertical, take out the test plate, and measure the length shifted from the coating site with a ruler (from the top of the coating surface to the coating Is preferably 5 mm or less, more preferably 2 mm or less, and still more preferably 0 mm.

Obtaining a coating film using the coating material of the present invention, for example, heating the coating material of the present invention or mechanically stirring to foam and drying to obtain a coating film gives a good appearance A coating film can be obtained.

<The coating film of this invention and its manufacturing method>
The present invention is also a coating film obtained using the paint of the present invention.
In addition, the coating film of this invention can be suitably obtained by drying, after heating and stirring the coating material of this invention, making it foam. Especially, by heating the coating material of this invention, it can dry, making a coating material foam, and can obtain the coating film of this invention more suitably.

The coating film of the present invention preferably has an average thickness of 2 to 8 mm. By setting it to 2 mm or more, the function required for the coating film can be more fully exhibited. Moreover, by making it 8 mm or less, drying property (especially heat drying property at the time of baking) will become a better thing, peeling of a coating film, generation | occurrence | production of a crack, etc. can be prevented, and a favorable coating film can be formed. The average thickness of the coating film is more preferably 6 mm or less, and still more preferably 5 mm or less.

The base material for forming the coating film of the present invention is not particularly limited as long as the coating film can be formed, and may be any metal material such as a steel plate, plastic material and the like. Especially, forming a coating film on the surface of a steel plate is one of the preferable usage forms of the coating film of this invention.

The coating film of the present invention can be obtained, for example, by applying the coating composition of the present invention using a brush, spatula, air spray, airless spray, mortar gun, ricin gun or the like.

The present invention is also a method for producing a coating film by heating and stirring the paint of the present invention to foam it and drying it. In other words, the present invention is a method for producing a coating film using a paint, characterized by comprising a step of stirring and / or heating the paint containing the resin composition and the pigment of the present invention. It is also the manufacturing method of the coating film to perform. Here, the paint used for stirring or heating is one in which lignins and / or lignin derivatives and a foaming agent component are blended, but the order of blending is not particularly limited. In addition, the stirring process can be performed using conventionally well-known instruments, such as a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, and a dissolver. The present invention is preferably a method for producing a coating film while foaming by heating and drying the paint of the present invention. In addition, when foaming is performed by heat-drying the paint, the foaming agent component is usually not mechanically foamed by stirring the paint before heat-drying. Moreover, in a heating process, it is preferable that the coating film formed by apply | coating the said coating material on a base material shall be 40-200 degreeC. More preferably, it is 90-180 degreeC, More preferably, it is 100-160 degreeC. You may pre-dry at low temperature before heat drying.
Moreover, it is preferable that the time which makes a coating film the said temperature is 1 to 300 minutes. More preferably, it is 2 to 250 minutes, and particularly preferably 10 to 150 minutes.

The coating film of the present invention can exhibit a desired function since various additive components are sufficiently dispersed, and is excellent in adhesion to a substrate and appearance. In addition, for example, when the coating film of the present invention is used as a vibration damping material, it can exhibit a significantly superior vibration damping property in a wide temperature range, so that it can be used for transportation vehicles such as automobiles, railway vehicles, ships, airplanes, and electrical equipment, It can be suitably used for building structures, construction equipment, and the like.

The vibration damping property of the coating film of the present invention can be evaluated by measuring the loss factor of the film.
The loss factor is usually expressed by η and indicates how much the vibration applied to the coating film is attenuated. The above loss factor indicates that the higher the numerical value, the better the damping performance.
The loss factor can be measured by the method described in Examples described later.

The paint of the present invention is excellent in dispersibility of various additive components, and can suitably form a coating film having excellent adhesion to the substrate and appearance.

It is a side surface schematic diagram of the test board used by the coating-film misalignment resistance test.

Hereinafter, the present invention will be described in more detail with reference to modes for carrying out the invention, but the present invention is not limited only to the modes for carrying out these inventions. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

In the following production examples, various resin properties were evaluated as follows.
<Average particle size>
The average particle size of the emulsion particles was measured using a particle size distribution measuring device (Otsuka Electronics FPAR-1000) by a dynamic light scattering method.
<Nonvolatile content (N.V.)>
About 1 g of the obtained emulsion was weighed, and after 150 ° C. for 1 hour with a hot air dryer, the remaining amount after drying was regarded as a non-volatile content, and the ratio to the mass before drying was expressed in mass%.
<PH>
The value at 25 ° C. was measured with a pH meter (“F-23” manufactured by Horiba, Ltd.).
<Viscosity>
Using a B-type rotational viscometer (“VISCOMETER TUB-10” manufactured by Toki Sangyo Co., Ltd.), the measurement was performed at 25 ° C. and 20 rpm.

<Weight average molecular weight of polymer>
It measured by GPC under the following measurement conditions.
Column used: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) were connected in series and used eluent: tetrahydrofuran (THF)
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object was dissolved in THF so that the solid content was about 0.2% by mass, and the sample was filtered through a filter.

<Lignin / Lignin derivative weight average molecular weight>
It measured by GPC under the following measurement conditions.
Column used: TOS guard column α, TSKgel α5000, α-4000, and α-3000 manufactured by Tosoh Corporation are connected in this order.
Eluent: A solution prepared by dissolving 44.5 g of boric acid in a solution of 1,800 g of acetonitrile and 7141.1 g of water and adjusting the pH to 10.0 with a 30% aqueous NaOH solution was used.
Sample injection amount: 100 μL
Flow rate: 1.0 mL / min
Column temperature: 40 ° C .;
Detector: Japan Waters, 2414 Differential refraction detector analysis software: Japan Waters, Empower2 Software;
Standard substance for preparing calibration curve: Polyethylene glycol Measurement method: Sample dissolved in the above eluent so that the concentration of lignin / lignin derivative is 0.5 mass%.

<Glass glass transition temperature (Tg)>
The Tg of the polymer was calculated from the monomer composition used in each stage using the following calculation formula (1).

In the formula, Tg ′ is Tg (absolute temperature) of the polymer. W ₁ ′, W ₂ ′,... Wn ′ are mass fractions of the respective monomers with respect to the total monomer components. T ₁ , T ₂ ,... Tn are glass transition temperatures (absolute temperatures) of a homopolymer (single polymer) composed of each monomer component.

In addition, Tg calculated from the monomer composition used in all stages was described as “total Tg”.
Tg values of the respective homopolymers used for calculating the glass transition temperature (Tg) of the polymerizable monomer component by the above formula (1) are shown below.
Methyl methacrylate (MMA): 105 ° C
Styrene (St): 100 ° C
2-ethylhexyl acrylate (2EHA): -70 ° C
Butyl acrylate (BA): -56 ° C
Acrylic acid (AA): 95 ° C

The mechanical foaming agent used in the following examples will be described.
The polyoxyethylene alkyl ether / sulfosuccinic acid half ester salt has the following formula (i):

(Wherein R represents a secondary alkyl group having 12 to 14 carbon atoms).
In the formula, n represents an average added mole number and is 9. In the present specification, this compound is also represented as polyoxyethylene alkyl ether / sulphosuccinic acid half ester salt (i).

The emulsifier used in the following examples will be described.
The polyoxyethylene alkyl ether, sulfosuccinate, disodium salt has the following formula (ii):

It is a compound represented by these. In the formula, n represents an average added mole number and is 8. In this specification, this compound is also represented as polyoxyethylene alkyl ether sulfosuccinate disodium salt (ii).
Lebenol WZ (trade name, sodium polyoxyethylene alkyl ether sulfate: manufactured by Kao Corporation)

(Production Example 1)
A polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. Meanwhile, 520 parts of methyl methacrylate, 230 parts of 2-ethylhexyl acrylate, 240 parts of butyl acrylate, 10 parts of acrylic acid, and 3 parts of t-dodecyl mercaptan (hereinafter also referred to as t-DM) as a polymerization chain transfer agent are added to the dropping funnel. A monomer emulsion consisting of 180 parts of polyoxyethylene alkyl ether, sulfosuccinate, disodium salt (ii) and 164 parts of deionized water, previously adjusted to a 20% aqueous solution, was charged. Next, while maintaining the internal temperature of the polymerization vessel at 75 ° C., 27 parts of the above monomer emulsion, 5 parts of 5% aqueous potassium persulfate solution and 10 parts of 2% aqueous sodium hydrogen sulfite solution were added, Polymerization was started. After 40 minutes, the remaining monomer emulsion was uniformly added dropwise over 210 minutes while maintaining the reaction system at 80 ° C. At the same time, 95 parts of a 5% aqueous potassium persulfate solution and 90 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 210 minutes, and the temperature was maintained for 60 minutes after completion of the addition to complete the polymerization.
After cooling the obtained reaction liquid to room temperature, 16.7 parts of 2-dimethylethanolamine was added, and the non-volatile content was 55.0%, pH 8.1, viscosity 190 mPa · s, average particle diameter 245 nm, weight average molecular weight 84000. An acrylic emulsion was obtained.

(Production Example 2)
A polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 100 parts of styrene, 420 parts of methyl methacrylate, 220 parts of 2-ethylhexyl acrylate, 250 parts of butyl acrylate, 10 parts of acrylic acid, 3 parts of t-dodecyl mercaptan, Lebenol WZ (previously adjusted to 20% aqueous solution) A monomer emulsion comprising 180 parts of a trade name, sodium polyoxyethylene alkyl ether sulfate (manufactured by Kao Corporation) and 164 parts of deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 75 ° C., 27 parts of the above monomer emulsion, 5 parts of 5% aqueous potassium persulfate solution and 10 parts of 2% aqueous sodium hydrogen sulfite solution were added, Polymerization was started. After 40 minutes, the remaining monomer emulsion was uniformly added dropwise over 210 minutes while maintaining the reaction system at 80 ° C. At the same time, 95 parts of a 5% aqueous potassium persulfate solution and 90 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 210 minutes, and the temperature was maintained for 60 minutes after completion of the addition to complete the polymerization.
After cooling the obtained reaction liquid to room temperature, 16.7 parts of 2-dimethylethanolamine was added, and styrene having a nonvolatile content of 55.0%, pH 8.0, viscosity of 290 mPa · s, particle diameter of 190 nm, and weight average molecular weight of 78,000. / An acrylic emulsion was obtained.

Example 1
To 77.7 parts of the emulsion obtained in Production Example 1, 19.4 parts of magnesium lignin sulfonate, 2.9 parts of a heating foaming agent (trade name F-36, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and 18.2 water The test sample 1 was obtained by mixing the parts.

(Example 2)
To 77.7 parts of the emulsion obtained in Production Example 2, 19.4 parts of sodium lignin sulfonate, 2.9 parts of a heating foaming agent (trade name F-36, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), and 18.2 water The test sample 2 was obtained by mixing the parts.

(Example 3)
58.3 parts of the emulsion obtained in Production Example 2 were mixed with 38.8 parts of sodium lignin sulfonate, 2.9 parts of a heating foaming agent (trade name F-36, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), and 34.2 parts of water. Parts were mixed to obtain test sample 3.

Example 4
To 75.5 parts of the emulsion obtained in Production Example 1, 18.9 parts of magnesium lignin sulfonate, 5.6 parts of a heating foaming agent (trade name F-36, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), and 20.0 water The test sample 4 was obtained by mixing the parts.

(Example 5)
To 77.7 parts of the emulsion obtained in Production Example 1, 19.4 parts of sodium lignin sulfonate, 2.9 parts of a heating foaming agent (trade name EXPANCEL WU642, manufactured by Nippon Philite Co., Ltd.), and water 18.2 Parts were mixed to obtain test sample 5.

(Example 6)
75.2 parts of the emulsion obtained in Production Example 2 were mixed with 18.8 parts of sodium lignin sulfonate and a mechanical foaming agent (polyoxyethylene alkyl ether / sulfosuccinic acid half ester salt (i) previously adjusted to a 20% aqueous solution) 6 0.0 parts and 11.6 parts of water were mixed to obtain test sample 6.

(Example 7)
72.3 parts of the emulsion obtained in Production Example 1 were mixed with 18.1 parts of magnesium lignin sulfonate and a mechanical foaming agent (polyoxyethylene alkyl ether / sulfosuccinic acid half ester salt (i) previously adjusted to a 20% aqueous solution) 9 .6 parts and 8.7 parts of water were mixed to obtain test sample 7.

(Comparative Example 1)
A test sample 8 was obtained by mixing 2.9 parts of a heating foaming agent (trade name F-36, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and 2.4 parts of water with 100 parts of the emulsion obtained in Production Example 2.

(Comparative Example 2)
The emulsion obtained in Production Example 2 was used as Test Sample 9.

(Preparation of damping material composition)
Test samples 1 to 9 obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were blended as follows, and the coating displacement resistance test, dry coating surface condition, and vibration damping properties were evaluated as blends. did. The results are shown in Table 1.
Test Samples 1 to 9 359 parts Calcium carbonate NN # 200 ^{* 1} 620 parts Dispersant Aquaric DL-40S ^{* 2} 6 parts Thickener Acryset WR-650 ^{* 3} 4 parts Antifoam Nopco 8034L ^{* 4} 1 part * 1: Nitto Flour Industry Co., Ltd. filler * 2: Nippon Shokubai Co., Ltd. polycarboxylic acid type dispersant (active ingredient 44%)
* 3: Nippon Shokubai Co., Ltd. Alkali-soluble acrylic thickener (active ingredient 30%)
* 4: Defoaming agent manufactured by San Nopco Co., Ltd. (main component: hydrophobic silicone + mineral oil)

(Paint displacement resistance test)
To the 0.8 mm * 70 mm * 150 mm steel plate (ED steel plate) electrodeposited using the cationic electrodeposition paint Electron “KG-400” manufactured by Kansai Paint Co., Ltd., the coating composition obtained as described above was applied to a wet film thickness of 6 mm. Then, the coated surface was immediately vertical and baked at 120 ° C. for 30 minutes, and the obtained coating film was visually observed to evaluate the coating film disintegration property (see FIG. 1). .) After heating, the test plate is taken out, the length shifted from the application site is measured with a ruler, and evaluated according to the following criteria.
Length of paint collapse from the upper end of the evaluation standard application surface (mm)
◎: 0 mm or more, 1 mm or less ○: 1 mm or more, 2 mm or less Δ: 2 mm or more, 5 mm or less ×: 5 mm or more

(Dry coating surface condition)
On a steel plate (trade name SPCC-SD, width 75 mm × length 150 mm × thickness 0.8 mm: manufactured by Nippon Test Panel Co., Ltd.), the prepared damping material composition was applied so that the coating thickness of the composition was 3 mm. did. Then, it dried for 30 minutes at 150 degreeC using the hot air dryer, and evaluated the surface state of the obtained dried coating film on the following references | standards.
Evaluation criteria ○: No abnormality △: Cracks on the surface or interface ×: Unable to maintain the coating film shape

(Vibration suppression test)
The above damping material composition is applied to a cold rolled steel sheet (SPCC, width 15 mm × length 250 mm × thickness 1.5 mm) at a thickness of 3 mm, dried at 150 ° C. for 30 minutes, and then coated on the cold rolled steel sheet. A damping material film having a density of 4.0 kg / m ² was formed. Measurement of vibration damping is performed by evaluating the loss factor at each temperature (20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C) using the cantilever method (loss factor measurement system manufactured by Ono Sokki Co., Ltd.). did. In addition, the evaluation of the vibration damping performance is performed based on the total loss factor (the sum of the loss factors at 20 ° C., 30 ° C., 40 ° C., 50 ° C., and 60 ° C.). It was supposed to be.

From the results described above, the resin composition of the present invention includes lignins and / or lignin derivatives, and further includes a foaming agent component, thereby being excellent in dispersibility of various additive components, It is clear that a coating film having an excellent appearance can be suitably formed and can be suitably applied to a wide variety of uses. In addition, since the resin composition of this invention has the outstanding damping property, it can be applied suitably also for a damping material use.
For example, when Example 2 and Comparative Example 1 are compared, the resin composition containing the foaming agent further contains inexpensive lignins and / or lignin derivatives, so that the adhesion, appearance, and control of the resulting coating film are reduced. It is clear that tremor is greatly improved.

Claims (9)

A resin composition comprising a lignin and / or a lignin derivative, and further comprising a foaming agent component. Content of the said foaming agent component is 300 mass% or less with respect to 100 mass% of mass of lignins and / or a lignin derivative, The resin composition of Claim 1 characterized by the above-mentioned. The resin composition according to claim 1, wherein the foaming agent component is a surfactant component and / or a heat-expandable capsule-type foaming agent. The resin composition according to any one of claims 1 to 3, wherein the composition further contains an emulsion polymer. 5. The resin composition according to claim 4, wherein the emulsion polymer includes at least one polymer selected from the group consisting of a (meth) acrylic polymer, a diene polymer, and a vinyl acetate polymer. . The resin composition according to claim 1, wherein the composition is for heat drying. A paint comprising the resin composition according to any one of claims 1 to 6 and a pigment. A coating film obtained by using the paint according to claim 7. A method of producing a coating film using a paint,
A method for producing a coating film, comprising a step of stirring and / or heating a paint containing the resin composition according to any one of claims 1 to 6 and a pigment.

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