JP2013199538A - Resin for heat-drying - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin for heat-drying which exhibits an excellent heat-drying property, and also an excellent damping property, and is suitably applied to various uses such as a damping material.SOLUTION: Polymer emulsion and cross-linked polymer emulsion are essential for resin for heat-drying. A polymer for forming the polymer emulsion has a weight-average molecular weight of 20,000-800,000. A polymer for forming the cross-linked polymer emulsion has a solubility parameter value different from the polymer for forming the polymer emulsion by 0.5 or more.

Description

The present invention relates to a heat drying resin. More specifically, a resin for heating and drying useful as a material for a vibration damping material used for preventing vibration and noise in various structures and keeping quietness, a thick film coating composition for heating and drying, and a composition formed thereby. It is related with the coating film.

Resin for heat drying is a material used to form a coating film that exhibits various functions on a base material by heat drying, and it is suitable for industrial production processes to form a coating film by heat drying. Used in the manufacture of many industrial products. In recent years, damping properties have attracted attention as one of new functions, and are also used for damping materials.
The damping material is for keeping vibration and noise in various structures and keeping quiet, for example, in addition to being used under the indoor floor of an automobile, a railway vehicle, a ship, an aircraft, an electrical device, Widely used in building structures and construction equipment. As a material used for such a damping material, conventionally, a molded product such as a plate-shaped molded body or a sheet-shaped molded body made of a material having vibration absorption performance and sound absorption performance has been used. On the other hand, when the shape of the place where vibration or sound is generated is complicated, it is difficult to apply these molded products to the place where vibration is generated. Various methods for exerting the effect have been studied. For example, asphalt sheets containing inorganic powder have been used under the floors of automobiles, etc., but since there is a need for heat-sealing, improvement in workability and the like is desired. Various compositions for damping materials and polymers to be formed have been studied.

As described above, coating-type damping materials (paints) have been developed as substitute materials for molded products, and, for example, by coating films formed by spraying or applying by any method to the corresponding locations. Various vibration-damping paints that can obtain a vibration absorbing effect and a sound absorbing effect have been proposed. Specifically, for example, as a water-based vibration-damping paint with improved coating film hardness obtained by blending a synthetic resin powder with a color developing agent such as asphalt, rubber, synthetic resin, and the like suitable for indoor use in automobiles, Anti-vibration coatings in which activated carbon is dispersed as a filler in a resin emulsion have been developed. However, even with these conventional products, the vibration damping performance is still not at a sufficiently satisfactory level, and there is a need for a technique that can further exhibit the vibration damping performance.

Under such circumstances, for the purpose of improving vibration damping performance, it is configured using a polymer composition including a low molecular material holding medium material composite including a low molecular material and a medium material and a polymer material. A damping material is disclosed (for example, see Patent Document 1). This is because a low molecular weight material is a softening material such as mineral oil, a plasticizer such as a phthalate ester, a tackifier, a lubricant such as an oligomer or paraffin, and a medium material having a number average molecular weight of 40,000 or more. A thermoplastic polymer or a thermosetting material is used as the plastic polymer organic material or the polymer material, and the difference in solubility parameter value between the low molecular material and the medium material is specified.
In addition, the weight average of individual Hildebrand solubility parameter values for the components of the liquid phase includes a dispersed phase containing fusible organic polymer particles and a liquid phase containing a plasticizer and an organic diluent. And plastisol differing by a specific value are disclosed (for example, see Patent Document 2). It is suitable for making into films and molded articles and as a coating material for various metal and non-metal substrates, and is said to be effective for adhering to substrates.

JP-A-7-324167 (pages 1 and 2) JP-T 2009-544817 (pages 1 and 2)

In recent years, emulsions are frequently used as heat-drying resins in consideration of environmental considerations, workability during coating film formation, safety for industrial products, and the like. In a coating material using an emulsion, water is volatilized after application, and emulsion particles (resin particles) are fused to form a coating film. When drying by heating, particularly when the film thickness is thick, the film is formed from the surface of the coating film, so-called skinning occurs, and water in the coating film is difficult to escape during drying. In addition, it is difficult for water to escape when trying to form a coating film that can exhibit suitable coating performance for various applications, or when drying by heating at hundreds of degrees Celsius to improve the drying speed. The heat drying property will be reduced. In the case of an emulsion coating film, performance such as water resistance is often required, but the heat drying property tends to decrease as the performance is improved. If the heat drying property is poor, problems such as bubbles are generated during drying. In particular, in applications such as damping materials, it is desirable to form a thick film to make the functions such as damping performance sufficient, but the thicker the film, the more heat drying the emulsion. It becomes difficult to make it good. If a good coating film is not formed such as generation of bubbles, various functions such as vibration damping performance cannot be fully expressed.
For this reason, the heat drying property is one of the important performance evaluation indexes in the heat drying resin that can be suitably applied to the damping material application.

However, in the techniques described in Patent Documents 1 and 2 described above, the above is not recognized as a problem, and thus various performances such as vibration damping properties are sufficiently obtained in the resin for heat drying using an emulsion. There was room for improvement in terms of improving the heat drying property for the purpose of expression. That is, in Patent Document 1, although the difference in solubility parameter value between the low molecular material and the medium material is specified, the emulsion is used as the polymer material, and the emulsion is devised for improving the heat drying property. It is not disclosed to do. In Patent Document 2, there is no disclosure of use for a damping material or the like, and there is no disclosure of devising for improving heat drying property.

The present invention has been made in view of the above-mentioned present situation, and the heat drying property of the polymer emulsion is improved, and accordingly, various performances such as vibration damping properties are excellent. Therefore, the present invention is suitable for various applications such as vibration damping materials. An object of the present invention is to provide a heat drying resin applied to the above.
Another object of the present invention is to provide a heat-drying thick film coating composition that is suitable for forming a thick film coating film, and a coating film formed thereby. Is.

The present inventor made various studies on the resin for heat drying, and first noticed that the water-based polymer emulsion was excellent in terms of workability and the like. When a polymer emulsion and a crosslinked polymer emulsion are used as emulsions having at least two different characteristics, the dryness resulting from the polymer emulsion and the toughness resulting from the crosslinked polymer emulsion are combined to form a thick film coating film. Even when formed, it was thought that heat drying property improved. And just by blending these two types of polymer emulsions with the polymer emulsion as the base resin and the cross-linked polymer emulsion as the blend resin, the effect of improving the heat drying property is not sufficient. If the solubility parameter values (hereinafter also referred to as SP values) of the polymer emulsions are made to be incompatible with each other, the different characteristics of each polymer emulsion will be sufficiently exhibited and the heat drying property will be improved. It was something that was found. In particular, heat-drying properties are improved by blending a certain amount of cross-linked polymer emulsions (SBR latex, NBR latex, cross-linked acrylic emulsion, etc.) with poor compatibility with emulsions for vibration damping materials (preferred form is low molecular weight, specific Tg). Will be. The base resin and blend resin are incompatible and each has a continuous structure, and it is estimated that the heat-drying property of the thick film has been improved by the effect of the base resin with good drying property and the tough blend resin. ing.
In addition, a thick film coating composition for heat drying having such a resin for heat drying as one of the essential components has improved heat drying properties when forming a thick film coating, resulting in a thick film coating. Can fully exhibit the various functions exhibited by the anti-vibration agent, and in particular, by using a coating composition for damping material, the coating film (damping material) formed by using the coating composition is extremely excellent in damping. It has also been found that it is very useful as a damping material for various structures. In this way, 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 for heating and drying which essentially comprises a polymer emulsion and a crosslinked polymer emulsion, and the polymer forming the polymer emulsion has a weight average molecular weight of 20,000 to 800,000, The polymer to be formed is a heat-drying resin having a solubility parameter value different from that of the polymer forming the polymer emulsion by 0.5 or more.
The present invention is described in detail below.

The heat drying resin of the present invention comprises a polymer emulsion and a crosslinked polymer emulsion as essential components.
Although it is desirable to mix and supply the polymer emulsion and the cross-linked polymer emulsion, they may be supplied separately. Since the heat drying resin forms a coating film by heat drying, it is sufficient that both are mixed in a state before drying at the time of coating film formation.
Each of the polymer emulsion and the crosslinked polymer emulsion may be one kind or two or more kinds. For example, in a polymer emulsion and a crosslinked polymer emulsion, when one or both of them contain two or more types of polymers, the numerical range relating to the difference in properties such as SP value is in the crosslinked polymer emulsion and at least one in the polymer emulsion. However, it is preferable that all the polymers in the polymer emulsion and all the polymers in the cross-linked polymer emulsion are in the numerical range.

In the present invention, “polymer emulsion” means an uncrosslinked polymer emulsion, and “crosslinked polymer emulsion” means a crosslinked polymer emulsion.
Moreover, it is preferable that a polymer emulsion contains the polymer (henceforth a polymer (A)) which forms a polymer emulsion, and an aqueous medium. Similarly, the crosslinked polymer emulsion preferably contains a crosslinked polymer forming the crosslinked polymer emulsion (hereinafter also referred to as polymer (B)) and an aqueous medium.

In the heat drying resin, the solubility parameter value (SP value) of the polymer (polymer (A)) forming the polymer emulsion and the polymer (polymer (B)) forming the crosslinked polymer emulsion is differentiated, The compatibility of the polymer (B) with the polymer (A) is deteriorated. Usually, if the SP value difference between polymers increases, the compatibility becomes worse. In the present invention, the SP value is different by 0.5 or more. The relationship between the SP value of the polymer forming the polymer emulsion and the SP value of the polymer forming the crosslinked polymer emulsion may be either larger or smaller, and the difference between the two obtained by subtracting the smaller from the larger SP value. May be 0.5 or more.
Thus, by setting the difference in SP value between the polymer (A) and the polymer (B) to 0.5 or more, the compatibility between the polymer (A) and the polymer (B) is reduced, When the polymer has a continuous structure in the coating film, and the effects of the polymer emulsion having good drying property and the tough crosslinked polymer emulsion are respectively expressed, the heat drying property of the coating film is improved.

The SP value difference is preferably 0.6 or more, and more preferably 0.9 or more. Moreover, when SP value difference becomes large too much, there exists a possibility that the compatibility between a polymer (A) and a polymer (B) may become low too much. For this reason, the respective polymers are separated and the interaction is lowered, so that sufficient heat drying property may not be exhibited. Therefore, the upper limit of the SP value difference is preferably 3.0 or less, and more preferably 2.0 or less.
In addition, the SP value of the polymer (A) and the polymer (B) is not particularly limited as long as the above SP value difference is satisfied, but it is preferable from the viewpoint of the affinity with the solvent and the effect on the formation of the coating film. Is 7.0 to 12.5, more preferably 8.0 to 12.0.

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

In the formula, δ is the SP value of the polymer. Δe ₁ is a calculated value (kcal / mol) of evaporation energy of each monomer component constituting the polymer, and ΣΔe ₁ is a total value of the calculated values of all monomer components constituting the polymer. is there. ΔV _m is a calculated value (ml / mol) of the molecular volume of each monomer component constituting the polymer, and ΣΔV _m is the sum of the calculated values of all the monomer components constituting the polymer. . x is a molar distribution of each component of the monomer constituting the polymer.
Note that normally used calculation values can be used for the evaporation energy of the monomer component and the molecular volume of the monomer component.
Thus, each SP value of a polymer (A) and a polymer (B) can be adjusted by adjusting the kind and structural ratio of the monomer to comprise, thereby, between polymers. It becomes possible to adjust the SP value difference.

The monomer component that is a raw material of the polymer (polymer (A)) forming the polymer emulsion in the present invention is not particularly limited as long as the effects of the present invention can be exhibited, but the unsaturated carboxylic acid single amount The body is preferably included. More preferably, it comprises an unsaturated carboxylic acid monomer and another monomer copolymerizable with the unsaturated carboxylic acid monomer. The unsaturated carboxylic acid monomer is not particularly limited as long as it is a compound having an unsaturated bond and a carboxyl group in the molecule, but preferably contains an ethylenically unsaturated carboxylic acid monomer.

In the present invention, the polymer (polymer (A)) forming the polymer emulsion may be one kind of polymer as described above, or may be composed of two or more kinds of polymers. Further, the polymer (A) may be composed of two or more kinds of polymers, and they may be combined. In addition, when the polymer (A) is in a form having a core part and a shell part to be described later, the unsaturated carboxylic acid monomer and the other monomer copolymerizable with the unsaturated carboxylic acid monomer are It may be contained in any of the monomer component forming the core part of the emulsion and the monomer component forming the shell part, and may be used in both of them.

The ethylenically unsaturated carboxylic acid monomer is not particularly limited. For example, (meth) acrylic acid, crotonic acid, itaconic acid, citraconic acid, fumaric acid, maleic acid, maleic anhydride, monomethyl fumarate, monoethyl One type or two or more types of unsaturated carboxylic acids such as fumarate, monomethyl maleate, monoethyl maleate, or derivatives thereof may be used. Among these, (meth) acrylic acid monomers such as (meth) acrylic acid are preferable. That is, the polymer (polymer (A)) forming the polymer emulsion is a (meth) acrylic polymer in which at least one of the monomer components is a (meth) acrylic acid monomer, 1 is one of the preferred embodiments of the present invention.

Among the above (meth) acrylic polymers, those obtained by using a monomer component containing a (meth) acrylic acid monomer are preferable. In the (meth) acrylic polymer of the present invention, at least one of the monomer components is C (R ¹ ) ₂ = CH-COOR ² or C (R ³ ) ₂ = C (CH ₃ ). A monomer that is a monomer represented by —COOR ⁴ (R ¹ , R ² , R ^3, and R ⁴ are the same or different and each represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group). It is preferable that it is obtained using components.
In the present specification, the (meth) acrylic acid monomer has 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, and A monomer having —COOH group, and a (meth) acrylic monomer has 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. And a monomer in the form in which the —COOH group is an ester or a salt, or a derivative of such a monomer.

The monomer component used as the raw material for the (meth) acrylic polymer is 0.1 to 20% by mass of the (meth) acrylic acid monomer with respect to 100% by mass of the total monomer components, and other common components. It preferably contains 99.9 to 80% by mass of a polymerizable ethylenically unsaturated monomer. By including the (meth) acrylic acid-based monomer, the dispersibility of fillers such as inorganic powders is improved in the later-described thick film coating composition for heat drying that requires the heat drying resin of the present invention. As a result, vibration control is improved. Moreover, it becomes easy to adjust the acid value, Tg, physical properties, etc. of a polymer by including another copolymerizable ethylenically unsaturated monomer. In the monomer component, even if the (meth) acrylic acid monomer is less than 0.1% by mass or more than 20% by mass, the monomer component is hardly stably copolymerized. There is a fear. The (meth) acrylic polymer contained in the heat drying resin of the present invention has an excellent heat drying property and control in an aqueous vibration damping material due to the synergistic effect of the monomer units formed from these monomers. It becomes possible to fully exhibit the vibration characteristics.
More preferably, 0.5 to 3% by mass of (meth) acrylic acid monomer and 99.5% of other copolymerizable ethylenically unsaturated monomer are used with respect to 100% by mass of all monomer components. It is comprising -97 mass%.
Other copolymerizable ethylenically unsaturated monomers include (meth) acrylic monomers other than (meth) acrylic acid monomers, unsaturated monomers having nitrogen atoms, and aromatic rings Examples include unsaturated monomers and other monomers copolymerizable with (meth) acrylic acid monomers.

Examples of (meth) acrylic monomers other than the above (meth) acrylic monomers 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 , Iso Cutyl 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, vinyl formate, vinyl acetate, vinyl propionate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and the like; These salts and esterification Etc., and it is preferred to use one or more of these.

The salt is preferably a metal salt, ammonium salt, organic amine salt or the like. 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 alkaline earth metal atoms such as calcium and magnesium; aluminum, Trivalent metal atoms such as iron are preferred. Further, as the organic amine salt, an alkanolamine salt such as an ethanolamine salt, a diethanolamine salt, or a triethanolamine salt, or a triethylamine salt is preferable.

As a monomer component used as the raw material of the said (meth) acrylic-type polymer, it contains 20 mass% or more of (meth) acrylic-type monomers with respect to 100 mass% of all monomer components. It is preferable. More preferably, it is 30 mass% or more.

Examples of the unsaturated monomer having an aromatic ring include styrene, α-methylstyrene, vinyl toluene, and ethyl vinyl benzene. Styrene is preferred.
That is, the polymer (polymer (A)) forming the polymer emulsion is a styrene (meth) acrylic polymer obtained from a monomer component containing styrene. One.

When the polymer (polymer (A)) forming the polymer emulsion contains a styrene (meth) acrylic polymer, 1 unsaturated monomer having an aromatic ring is added to 100% by mass of all monomer components. It is preferable to contain -60 mass%. More preferably, it is 5-55 mass%.

Examples of the unsaturated monomer having a nitrogen atom include acrylonitrile, methacrylonitrile, 2-vinylpyrrolidone, acryloylmorpholine, acrylamide, methacrylamide, and diacetone acrylamide. Acrylonitrile is preferred.
When the unsaturated monomer having the nitrogen atom is included, the content ratio is preferably 0.1 to 5.0% by mass with respect to 100% by mass of all monomer components. More preferably, it is 0.3-4.0 mass%, More preferably, it is 0.5-3.0 mass%.

The polymer (polymer (A)) forming the polymer emulsion is preferably obtained from a monomer component containing a polar group-containing monomer. When the polymer (A) has a polar group, the interaction between the polymers in the damping material becomes larger, and the friction between the polymers becomes larger, so that the damping performance is more fully exhibited. Become.
The polar group contained in the polar group-containing monomer is not particularly limited as long as it is generally a polar group in an organic compound, but is selected from the group consisting of a hydroxyl group, a nitrile group, a carboxyl group, an amide group, and a pyrrolidone group. It is preferable that there is at least one. More preferably, it is a nitrile group and / or a carboxyl group.

The monomer component forming the (meth) acrylic polymer may contain an unsaturated monomer having a functional group. Examples of the functional group in the unsaturated monomer having the functional group include an epoxy group, a glycidyl group, an oxazoline group, a carbodiimide group, an aziridinyl group, an isocyanate group, a methylol group, a vinyl ether group, a cyclocarbonate group, and an alkoxysilane group. Is mentioned. One kind of these functional groups may be present in one molecule of the unsaturated monomer, or two or more kinds thereof may be present. Examples thereof include glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate and acrylic glycidyl ether, and these may be used alone or in combination of two or more.

The polymer (polymer (A)) forming the polymer emulsion has a weight average molecular weight of 20,000 to 800,000. In order for the polymer to exhibit functionality in various applications, such a molecular weight range is preferable. In particular, in order to exhibit vibration damping properties, it is preferable to change the energy of vibration applied to the polymer to thermal energy due to friction, and the polymer can move when vibration is applied to the polymer. It is necessary to be. When the polymer (A) has such a weight average molecular weight, the polymer can sufficiently move when vibration is applied, and high damping properties can be exhibited. The weight average molecular weight of the polymer (A) is more preferably 30,000 to 400,000, still more preferably 40,000 to 400,000, and particularly preferably 40,000 to 200,000.

The weight average molecular weight (Mw) can be determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

The polymer (polymer (A)) forming the polymer emulsion preferably has a glass transition temperature of -20 to 40 ° C. When a polymer (A) having such a glass transition temperature is used, the polymer (A) is suitable for application to various applications, and in particular, the damping performance in the practical temperature range of the damping material is effectively reduced. It can be expressed. The glass transition temperature of the polymer (A) is more preferably -15 to 35 ° C, still more preferably -10 to 30 ° C.
The glass transition temperature (Tg) may be determined based on the knowledge already obtained, and may be controlled by the type and use ratio of the monomer component described later. It can be calculated from the following 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 homopolymers (homopolymers) composed of the respective monomer components.

The polymer (polymer (B)) forming the crosslinked polymer emulsion in the present invention is not particularly limited as long as it has a crosslinked structure and can exhibit the effects of the present invention. For example, acrylonitrile butadiene rubber (NBR) ), Methyl methacrylate butadiene rubber (MBR), diene rubbers such as styrene butadiene rubber (SBR); cross-linked (meth) acrylic polymers, cross-linked styrene (meth) acrylic polymers, and the like.

About the diene rubber, among those used in various coating film forming applications, those satisfying the SP value in relation to the polymer emulsion, preferably various preferred described in the present specification What meets the condition may be applied.
About the above-mentioned crosslinked (meth) acrylic polymer and crosslinked styrene (meth) acrylic polymer, the above-described (meth) acrylic polymer and the monomer component forming the styrene (meth) acrylic polymer are multifunctional. It is preferable that it is prepared by adding a polymerizable unsaturated monomer.

Examples of the polyfunctional unsaturated monomer include trimethylolpropane tri (meth) acrylate, divinylbenzene, ethylene glycol di (meth) acrylate, N-methoxymethyl (meth) acrylamide, and N-methoxyethyl (meth). Acrylamide, Nn-butoxymethyl (meth) acrylamide, Ni-butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, diallyl phthalate, diallyl terephthalate, polyethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,6-hexanedio Rudi (meth) acrylate, neopentyl glycol di (meth) acrylate, triallyl cyanurate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, allyl acrylate, allyl And methacrylate. These may be used alone or in combination of two or more.

In the monomer component forming the crosslinked (meth) acrylic polymer and the crosslinked styrene (meth) acrylic polymer, the content of the polyfunctional unsaturated monomer is based on 100% by mass of the monomer component. It is preferable that it is 0.01-20 mass%. More preferably, it is 0.03-15 mass%, More preferably, it is 0.1-10 mass%.

In the present invention, the polymer (polymer (B)) forming the crosslinked polymer emulsion may be one kind of polymer as described above, or may be composed of two or more kinds of polymers. Further, the polymer (B) may be composed of two or more kinds of polymers, and a composite form thereof. When the polymer (B) has a core part and a shell part, the polymer (B) comprises two kinds of polymers, one of the two kinds of polymers being a core part and the other being a shell part. It may be formed.

The polymer (polymer (B)) that forms the crosslinked polymer emulsion preferably has a weight average molecular weight of 200,000 or more. By using a material having such a weight average molecular weight, various functions can be enhanced. For example, the vibration damping property of the resin composition can be further enhanced. More preferably, it is 300,000 or more, More preferably, it is 400,000 or more. The weight average molecular weight of the polymer (B) can be measured by the same method as described above.

The polymer (polymer (B)) forming the crosslinked polymer emulsion preferably has a glass transition temperature of -40 to 100 ° C. When the polymer (B) having such a glass transition temperature is used, for example, the damping performance in the practical temperature range of the damping material can be effectively expressed. The glass transition temperature of the polymer (B) is more preferably −35 to 70 ° C., and further preferably −30 to 50 ° C. The glass transition temperature of the polymer (B) can also be determined by the same method as described above.

Moreover, in the resin for heat drying of this invention, it is preferable that the difference of the glass transition temperature of a polymer (A) and a polymer (B) is 0-70 degreeC. Thus, by providing a difference in the glass transition temperature (Tg), for example, when applied to a damping material application, it becomes possible to express higher damping properties under a wide temperature range, and in particular, a practical range. Therefore, the vibration damping property in the 20 to 60 ° C. region is remarkably improved. The difference in glass transition temperature (Tg) is more preferably 0 to 60 ° C, still more preferably 0 to 50 ° C. In addition, as a polymer (A) and a polymer (B), when one or both contains 2 or more types of polymers, at least 1 type of one polymer and at least 1 type of the other polymer The difference in the glass transition temperature between the polymer (A) and all the polymers (B) contained in the resin is within the above range. More preferred.
However, as will be described later, when one or both of the polymer (A) and the polymer (B) is an emulsion having a core part and a shell part, the Tg and shell of the polymer forming the core part When there is a sufficient difference of 10 ° C. or more from the Tg of the polymer forming the part, and thereby high vibration damping properties can be expressed under a wide temperature range, the core shell The difference between the Tg of the whole polymer forming the emulsion and the Tg of the other polymer as a whole is preferably smaller, and is preferably 10 ° C. or lower.

One preferred form of the resin for heat drying is a form of emulsion particles in which at least one of a polymer forming a polymer emulsion and a polymer forming a crosslinked polymer emulsion has a core part and a shell part. More preferably, the polymer forming the polymer emulsion is in the form of emulsion particles having a core portion and a shell portion. Thereby, the interface between resin can be increased and effects, such as a damping improvement, can be enlarged more.

When the resin for heat drying of the present invention contains emulsion particles having a core part and a shell part, the core part and the shell part may be completely compatible, and may have a homogeneous structure in which they cannot be distinguished, These may be a core-shell composite structure or a microdomain structure in which they are not completely compatible but formed inhomogeneously, but among these structures, the characteristics of the emulsion can be fully extracted, and a stable emulsion can be obtained. In order to produce it, a core-shell composite structure is preferred.
An emulsion having a core-shell composite structure is excellent in vibration damping properties in a wide range within a practical temperature range. Especially in the high temperature range, it exhibits excellent vibration damping performance compared to other forms of vibration damping composition. As a result, within the practical temperature range, the vibration damping performance covers a wide range from room temperature to high temperature range. Can be demonstrated.
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.

When at least one of the polymer forming the polymer emulsion and the polymer forming the crosslinked polymer emulsion is in the form of emulsion particles having a core part and a shell part, a polymer obtained from the monomer component forming the core part; The difference in glass transition temperature (Tg) from the polymer obtained from the monomer component forming the shell part is the same as the difference in glass transition temperature between the polymer (A) and the polymer (B) described above. Is preferred.
Moreover, it is preferable that Tg of the polymer obtained from the total monomer component which combined the monomer component which forms a core part, and the monomer component which forms a shell part is -20-40 degreeC. More preferably, it is -10-30 degreeC.
The emulsion particles having the core part and the shell part can be obtained by using an emulsion polymerization method (multistage polymerization) described later.

The polymer (A) and polymer (B) contained in the heat drying resin of the present invention are present in the form of an emulsion, but the average particle diameter of each emulsion particle is preferably 50 to 450 nm.
By using emulsion particles with an average particle size in this range, the basic properties such as heat drying properties and coating properties required for vibration damping materials will be sufficient, and vibration damping properties will be even better. It can be. The upper limit is more preferably 400 nm or less, still more preferably 350 nm or less. When the average particle diameter of the emulsion particles is within such a range, the effect of the heat drying resin of the present invention is more effectively exhibited. Further, the lower limit of the average particle diameter is more preferably 80 nm or more, and further preferably 100 nm or more.
The average particle size (volume average particle size) can be determined by, for example, diluting the emulsion with distilled water, sufficiently stirring and mixing, and collecting about 10 ml in a glass cell, and measuring the particle size distribution analyzer (Particle) by the dynamic light scattering method. It can be determined by measuring with “NICOMP Model 380” manufactured by Sizing Systems.

In the heat drying resin of the present invention, 10 to 100 parts by mass of a polymer (polymer (B)) forming a crosslinked polymer emulsion is contained with respect to 100 parts by mass of the polymer (polymer (A)) forming the polymer emulsion. It is preferable to do. With such a content ratio, the heat drying property is more sufficiently exhibited, and the superior vibration damping property is exhibited. The content of the polymer (B) with respect to 100 parts by mass of the polymer (A) is more preferably 20 to 80 parts by mass, still more preferably 25 to 70 parts by mass.

The resin for heat drying of the present invention may contain other components as long as it contains a polymer emulsion and a crosslinked polymer emulsion.
When other components are included, the proportion of the other components is preferably 10% by mass or less, and more preferably 5% by mass or less, with respect to the entire heat drying resin. In addition, the other component here means a non-volatile content (solid content) remaining in the coating film even after the resin for heat drying is applied and heat-dried, and does not include an aqueous medium.
The resin for heat drying of the present invention preferably has a solid content of 40 to 80% by mass, more preferably 50 to 70% by mass, based on the entire resin.
In addition, solid content here means components other than the aqueous medium contained in resin for heat-drying.

Although it does not specifically limit as pH of resin for heat drying of this invention, It is preferable that it is 2-10, More preferably, it is 3-9, More preferably, it is 7-8. The pH of the resin composition can be adjusted by adding ammonia water, water-soluble amines, aqueous alkali hydroxide solution, or the like to the resin composition.
In this specification, pH can be measured with a pH meter. For example, it is preferable to measure the value at 25 ° C. using a pH meter (“F-23” manufactured by Horiba, Ltd.).

Although it does not specifically limit as viscosity of resin for heat drying of this invention, It is preferable that it is 1-10000 mPa * s, More preferably, it is 5-1000 mPa * s, More preferably, it is 5-500 mPa * s.
The viscosity can be measured using a B-type rotational viscometer under the conditions of 25 ° C. and 20 rpm.

As a method for producing the polymer contained in the heat drying resin of the present invention, the monomer component is polymerized by an emulsion polymerization method in the presence of an emulsifier, but the form for carrying out the emulsion polymerization is particularly limited. For example, it can be carried out by adding a monomer component, a polymerization initiator and an emulsifier as appropriate in an aqueous medium and polymerizing. Moreover, it is preferable to use a polymerization chain transfer agent or the like for molecular weight adjustment.

When the polymer contained in the heat drying resin of the present invention is an emulsion having a core part and a shell part, it is preferably obtained by using an ordinary emulsion polymerization method. Specifically, after the monomer component is emulsion-polymerized in an aqueous medium in the presence of an emulsifier and / or protective colloid to form a core part, the monomer component is further emulsion-polymerized into an emulsion containing the core part. It is preferably obtained by multistage polymerization that forms a shell portion. Thus, the polymer contained in the heat drying resin of the present invention is an emulsion having a core part and a shell part, and after the emulsion forms the core part, it is obtained by multistage polymerization that forms the shell part. The form that can be obtained is also one of the preferred forms of the present invention.

The aqueous medium is not particularly limited. For example, water, one or two or more mixed solvents that can be mixed with water, and a mixed solvent in which water is a main component in such a solvent. Etc. Among these, water is preferable in consideration of safety and environmental influence when applying the paint containing the heat drying resin of the present invention.

The amount of the emulsifier used is preferably 0.1 to 10% by mass with respect to 100% by mass of the total amount of compounds having a polymerizable unsaturated bond group. If it is less than 0.1% by mass, the mechanical stability cannot be sufficiently improved and the polymerization stability may not be sufficiently maintained. More preferably, it is 0.5-5 mass%, More preferably, it is 1-3 mass%.

As the emulsifier, one or more of anionic, cationic, nonionic and amphoteric surfactants and a polymeric surfactant can be used.
The anionic surfactant is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether sulfate, polyoxyalkylene oleyl ether sulfate sodium salt, polyoxyalkylene alkylphenyl ether sulfate, alkyl diphenyl ether disulfonate, poly Oxyalkylene (mono, di, tri) styryl phenyl ether sulfate, polyoxyalkylene (mono, di, tri) benzyl phenyl ether sulfate, alkenyl succinate; sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium alkyl sulfate Alkyl sulfate salts such as sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; Alkyl sulfonates such as sodium salts; alkyl sulfonates such as sodium dodecylbenzene sulfonate and alkali metal sulfates of alkali phenol hydroxyethylene; high alkyl naphthalene sulfonates; naphthalene sulfonic acid formalin condensates; sodium laurate, triethanolamine oleate, tri Fatty acid salts such as ethanolamine abietate; polyoxyalkyl ether sulfate ester; polyoxyethylene carboxylic ester sulfate salt; polyoxyethylene phenyl ether sulfate ester; succinic acid dialkyl ester sulfonate salt; polyoxyethylene alkyl aryl sulfate Examples include salts. These 1 type (s) or 2 or more types can be used.

Examples of commercially available products suitable as the anionic surfactant include Latemul WX, Latemuru 118B, Perex SS-H, Emulgen A-60, B-66, Lebenol WZ (manufactured by Kao Corporation), New Coal 707SF, New Coal 707SN, New Call 714SF, New Call 714SN, AB-26S, ABEX-2010, 2020, 2030, DSB (manufactured by Rhodia Nikka Co., Ltd.) and the like.
In addition, surfactants corresponding to these nonionic types can also be used.

As the above anionic surfactants, reactive surfactants, reactive anionic surfactants, sulfosuccinate type reactive anionic surfactants, alkenyl succinate type reactive anionic surfactants, etc. 1 type (s) or 2 or more types can be used.
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-2 (Products) Name, manufactured by Sanyo Kasei Kogyo Co., Ltd.), ADEKA rear soap SR-10, SR-20, SR-30 (manufactured by ADEKA) and the like.
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.
Furthermore, (meth) acrylic acid polyoxyethylene sulfonate salt (for example, “Eleminol RS-30” manufactured by Sanyo Chemical Industries, “Antox MS-60” manufactured by Nippon Emulsifier Co., Ltd.), allyloxymethylalkyloxypolyoxy Sulfate ester (salt) having an allyl group such as sulfonate salt of ethylene (for example, “Aqualon KH-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ammonium polyoxyalkylene alkenyl ether sulfate (for example, “Latemul PD-” manufactured by Kao Corporation 104 "etc.) can also be used.

Further, as the anionic surfactant, the following surfactants and the like can be used as the reactive surfactant.
Sulfoalkyl (carbon number 1 to 4) ester salt type surfactant of aliphatic unsaturated carboxylic acid having 3 to 5 carbon atoms, for example, 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium (Meth) acrylic acid sulfoalkyl ester salt type surfactants such as salts; sulfopropylmaleic acid alkylester sodium salt, sulfopropylmaleic acid polyoxyethylene alkylester ammonium salt, sulfoethylfumaric acid polyoxyethylene alkylester ammonium salt, etc. Aliphatic unsaturated dicarboxylic acid alkyl sulfoalkyl diester salt surfactants.

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. 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.

Among the above surfactants, it is preferable to use a non-nonylphenyl type surfactant from the environmental viewpoint.
The amount of the surfactant used may be appropriately set according to the type of surfactant to be used, the type of monomer component, and the like. From the viewpoint of stability of emulsion particles generated during emulsion polymerization, for example, heavy It is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, still more preferably 100 parts by weight of the total amount of monomer components used to form the coalesced. 1 to 3 parts by mass.

Examples of the protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose salt; natural polysaccharides such as guar gum Etc., and one or more of these can be used. The protective colloid may be used alone or in combination with a surfactant.
The use amount of the protective colloid may be appropriately set according to use conditions and the like. For example, 5 parts by mass or less with respect to 100 parts by mass of the total amount of monomer components used to form the polymer. It is preferable that it is 3 mass parts or less.

The polymerization initiator is not particularly limited as long as it is a substance that decomposes by heat and generates radical molecules, but a water-soluble initiator is preferably used. For example, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; water-soluble such as 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid) Thermal decomposition initiators such as hydrogen peroxide; hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide and Rongalite, potassium persulfate and metal salts, redox polymerization of ammonium persulfate and sodium bisulfite, etc. An agent etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The amount of the polymerization initiator used is not particularly limited and may be set as appropriate according to the type of the polymerization initiator. For example, the total amount of monomer components used to form the polymer is 100 parts by mass. It is preferable that it is 0.1-2 mass parts with respect to this, More preferably, it is 0.2-1 mass part.

In order to promote emulsion polymerization, the polymerization initiator may be used in combination with a reducing agent as necessary. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; for example, reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. These 1 type (s) or 2 or more types can be used.
It does not specifically limit as the usage-amount of the said reducing agent, For example, it is preferable that it is 0.05-1 mass part with respect to 100 mass parts of total amounts of the monomer component used in forming a polymer.

The polymerization chain transfer agent is not particularly limited. For example, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan; carbon tetrachloride , Halogenated hydrocarbons such as carbon tetrabromide and ethylene bromide; mercaptocarboxylic acid alkyl esters such as mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopyropionic acid tridecyl ester; mercaptoacetic acid methoxybutyl Mercaptocarboxylic acid alkoxyalkyl ester such as ester, mercaptopropionic acid methoxybutyl ester; carboxylic acid mercaptoal such as octanoic acid 2-mercaptoethyl ester Glycol ester or, alpha-methylstyrene dimer, terpinolene, alpha-terpinene, .gamma.-terpinene, dipentene, anisole, allyl alcohol and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan. The amount of the polymerization chain transfer agent used is, for example, preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less, with respect to 100 parts by mass of all monomer components.

The emulsion polymerization may be performed in the presence of a chelating agent such as sodium ethylenediaminetetraacetate, a dispersant such as sodium polyacrylate, an inorganic salt, or the like, if necessary. Moreover, as addition methods, such as a monomer component and a polymerization initiator, methods, such as a batch addition method, a continuous addition method, a multistage addition method, are applicable, for example. Moreover, you may combine these addition methods suitably.

Regarding the emulsion polymerization conditions in the above production method, the polymerization temperature is not particularly limited, and is preferably 0 to 100 ° C., and more preferably 40 to 95 ° C., for example. Also, the polymerization time is not particularly limited, and is preferably 1 to 15 hours, and more preferably 5 to 10 hours, for example.
The addition method of the monomer component, the polymerization initiator, and the like is not particularly limited, and for example, a batch addition method, a continuous addition method, a multistage addition method, or the like can be applied. Moreover, you may combine these addition methods suitably.

In the method for producing a polymer contained in the heat drying resin of the present invention, it is preferable to neutralize the emulsion with a neutralizing agent after producing the emulsion by emulsion polymerization. As a result, the emulsion is stabilized.
The neutralizing agent is not particularly limited, and for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; diglycolamine, aqueous ammonia; sodium hydroxide and the like can be used. These may be used alone or in combination of two or more. Among these, since the water resistance of the coating film formed from the later-described thick film coating composition for heating and drying, which requires the resin for heating and drying, is improved, a volatile base that volatilizes when the coating film is heated is used. It is preferable. More preferably, an amine having a boiling point of 80 to 360 ° C. is preferably used because heat drying properties are improved and vibration damping properties are improved. As such a neutralizing agent, for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, and diglycolamine are preferable. More preferably, an amine having a boiling point of 130 to 280 ° C is used.
In addition, the said boiling point is a boiling point in a normal pressure.

The heat drying resin of the present invention can constitute a thick film coating composition for heat drying together with other components as necessary. The thick film coating composition for heat drying comprising the heat drying resin, pigment, foaming agent and thickener of the present invention as essential components is also one aspect of the present invention. Such a thick film coating composition for heat drying, which essentially comprises the heat drying resin of the present invention, has excellent heat drying properties, can exhibit various functions, and has particularly excellent vibration damping properties. The damping material which can be exhibited can be formed.

The heat-drying thick film coating composition preferably contains, for example, 40 to 90% by mass, more preferably 50%, based on a total amount of 100% by mass of the heat-drying thick film coating composition. It is -90 mass%, More preferably, it is 60-90 mass%.
The blending amount of the heat-drying resin in the heat-drying thick film paint composition is, for example, that the solid content of the heat-drying resin is 10 to 60 with respect to 100% by mass of the solid content of the heat-drying thick film paint composition. It is preferable to set so that it may become mass%, More preferably, it is 15-60 mass%.

The pH of the thick film coating composition for heat drying is preferably 7-11, more preferably 7-9. The pH can be measured by the same method as described above.
The viscosity of the thick film coating composition for heat drying is preferably 50 to 200 Pa · s. With such a viscosity, it is suitable as a thick film coating composition for coating-type heating and drying, which is easy to apply to a substrate and has no dripping. More preferably, it is 60-150 Pa.s.
The viscosity of the thick film coating composition for heat drying can be measured by the same method as described above.

As said pigment, 1 type (s) or 2 or more types, such as the coloring agent mentioned later and a rust preventive pigment, can be used, for example. As a compounding quantity of the said pigment, it is preferable to set it as 50-700 mass parts with respect to 100 mass parts of solid content of heat drying resin, More preferably, it is 100-550 mass parts.

As the foaming agent, for example, a low-boiling hydrocarbon encapsulated heated expansion capsule, an organic foaming agent, an inorganic foaming agent, and the like are suitable, and one or more of these can be used. Examples of the heated expansion capsule include Matsumoto Microsphere F-30, F-50 (manufactured by Matsumoto Yushi Co., Ltd.); EXPANSELL WU642, WU551, WU461, DU551, DU401 (manufactured by Nippon Expandcel). Examples of the organic foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N-dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazine, p-oxybis (benzenesulfohydrazide), and the like. Examples of the foaming agent include sodium bicarbonate, ammonium carbonate, silicon hydride and the like.
As a compounding quantity of the said foaming agent, it is preferable to set it as 0.5-5.0 mass parts with respect to 100 mass parts of solid content of the resin for heat-drying, More preferably, it is 1.0-3.0 mass parts. is there.

Examples of the thickener include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like. As a compounding quantity of a thickener, it is preferable to set it as 0.01-2 mass parts by solid content with respect to 100 mass parts of solid content of the resin for heat drying, More preferably, it is 0.05-1.5 mass parts. More preferably, it is 0.1-1 mass part.

In addition, as other components that can be blended in the thick film coating composition for heat drying of the present invention, for example, a solvent; an aqueous crosslinking agent; a filler; a dispersant; an antifoaming agent; a colorant; Plasticizers; stabilizers; wetting agents; antiseptics; antifoaming agents; anti-aging agents; antifungal agents; ultraviolet absorbers; antistatic agents and the like, and one or more of these can be used. .
In addition, the said other component can be mixed with the said resin for heat drying etc. using a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver etc., for example.

Examples of the solvent include ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, and the like. What is necessary is just to set suitably as a compounding quantity of a solvent so that the solid content density | concentration of the heat drying resin in the thick film coating composition for heat drying may become the range mentioned above.

Examples of the aqueous crosslinking agent include oxazoline compounds such as Epocross WS-500, WS-700, K-2010, 2020, 2030 (all trade names, manufactured by Nippon Shokubai Co., Ltd.); Adeka Resin EMN-26-60, EM- Epoxy compounds such as 101-50 (Brand name, manufactured by ADEKA); Melamine compounds such as Cymel C-325 (Brand name, manufactured by Mitsui Cytec); Block isocyanate compounds; AZO-50 (Brand name, 50% by mass) Zinc oxide compounds such as zinc oxide aqueous dispersion (manufactured by Nippon Shokubai Co., Ltd.) are preferred. As a compounding quantity of a water-system crosslinking agent, it is preferable to set it as 0.01-20 mass parts by solid content with respect to solid content of 100 mass parts of resin for heat drying, for example, More preferably, 0.15-15 mass part More preferably, it is 0.5 to 15 parts by mass.
The water-based crosslinking agent may be added to the heat-drying resin, or may be added simultaneously when other components are blended as the heat-drying thick film coating composition. By mixing a crosslinking agent with the heat drying resin or composition, the toughness of the resin is improved, and as a result, a sufficiently high vibration damping property is exhibited in a high temperature region. Among them, it is preferable to use an oxazoline compound.

Examples of the filler include inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, titanium oxide, glass talk, magnesium carbonate, aluminum hydroxide, talc, diatomaceous earth, and clay; glass Examples of such inorganic fillers include flakes and mica; and fibrous inorganic fillers such as metal oxide whiskers and glass fibers. As a compounding quantity of a filler, it is preferable to set it as 50-700 mass parts with respect to 100 mass parts of solid content of resin for heat-drying, More preferably, it is 100-550 mass parts.

Examples of the dispersant include inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and organic dispersants such as polycarboxylic acid-based dispersants.
Examples of the antifoaming agent include silicon-based antifoaming agents.
Examples of the colorant include organic or inorganic colorants such as titanium oxide, carbon black, dial, hansa yellow, benzine yellow, phthalocyanine blue, and quinacridone red.
Examples of the rust preventive pigment include a metal phosphate, a metal molybdate, and a metal borate.

As the other component, a polyvalent metal compound may be used. In this case, the polyvalent metal compound improves the stability, dispersibility, heat drying properties of the thick film coating composition for heat drying, and the vibration damping properties of the vibration damping material formed from the thick film coating composition for heat drying. Will be. It does not specifically limit as a polyvalent metal compound, For example, zinc oxide, zinc chloride, zinc sulfate etc. are mentioned, These 1 type (s) or 2 or more types can be used.
Examples of the form of the polyvalent metal compound may include a powder, an aqueous dispersion, an emulsion dispersion, and the like. Among them, it is preferable to use in the form of an aqueous dispersion or an emulsified dispersion, and more preferably to use in the form of an emulsified dispersion because dispersibility in the thick film coating composition for heat drying is improved. is there.
Moreover, it is preferable that the usage-amount of a polyvalent metal compound shall be 0.05-5.0 mass parts with respect to 100 mass parts of solid content in the thick film coating composition for heat drying, More preferably, it is 0.00. It is 05-3.5 mass parts.

Moreover, the coating film obtained by apply | coating and drying the thick film coating composition for heat-drying is also one of this invention. The film thickness (after drying) of the coating film is preferably 1 to 10 mm.
The said thick film coating composition for heat-drying can form the coating film used as a damping material by apply | coating to a base material and drying, for example. As a method of applying the thick film coating composition for heat drying to the substrate, for example, it can be applied using a brush, a spatula, an air spray, an airless spray, a mortar gun, a lysine gun or the like.

The coating amount of the heat-drying thick film coating composition may be appropriately set depending on the application, desired performance, etc.For example, in order to exhibit sufficient functions such as vibration damping, The film thickness is preferably 1 mm or more, more preferably 2 mm or more. Moreover, it is preferable to make it the film thickness of the coating film after drying become 10 mm or less from the point of the drying property of a coating film, More preferably, it is 7 mm or less.
It is also preferable that the surface density of the coating film after drying is coated to a 1.0~7.0kg / ^{m 2,} more preferably from 2.0~6.0kg / ^{m 2.} In addition, by using the thick film paint composition for heating and drying of the present invention, it is possible to obtain a coating film that hardly causes expansion and cracks at the time of drying and after drying, and that hardly causes the paint on the inclined surface to slide off. It becomes.
Thus, the coating method of the thick film coating composition for heat drying which coats and dries so that the film thickness of the coating film after drying is 1 to 10 mm, and the surface density of the coating film after drying is The coating method of the thick film coating composition for heat drying which is applied and dried so as to be 2.0 to 6.0 kg / m ² is also one of the preferred embodiments of the present invention.

Since the resin for heat drying of the present invention has the above-described configuration, it exhibits excellent heat drying properties, and further has excellent vibration damping properties, and can be suitably used for various applications such as vibration damping materials. it can.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

In the following examples, various physical properties and the like were evaluated as follows.
<Solubility parameter (SP value)>
As described above, the SP value of each polymer forming each emulsion is determined by Fedors (Polymer Eng. Sci., 14, No. 2, 147, 1974) and Tortorello et al. (J. Coat. Technol., 55, 696). , 99, 1983).

<Glass transition temperature (Tg)>
It calculated using the formula (1) mentioned above from the monomer composition used at each stage.
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
Butyl acrylate (BA): -56 ° C
2-ethylhexyl acrylate (2EHA): -70 ° C
Acrylic acid (AA): 95 ° C

<Nonvolatile content (N.V.)>
About 1 g of the obtained emulsion was weighed, and after 110 hours at 110 ° C. 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.

<Average particle size>
The volume average particle diameter was measured using a particle size distribution measuring apparatus (“NICOMP Model 380” manufactured by Particle Sizing Systems) by a dynamic light scattering method.
<Weight average molecular weight>
It measured by GPC (gel permeation chromatography) on the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The molecular weight was measured using a measurement sample dissolved in THF so that the solid content was about 0.2% by mass and filtered through a filter.

In the following emulsion preparation and examples, Emulsion A is a polymer emulsion and Emulsion B is a cross-linked polymer emulsion. However, Emulsion B in Production Example 7 is a non-crosslinked polymer emulsion.

Production Example 1 (Production of Emulsion A)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, 456 parts of methyl methacrylate, 534 parts of butyl acrylate, 10 parts of acrylic acid, 5 parts of t-dodecyl mercaptan, Lebenol WZ (trade name, manufactured by Kao Corporation, polyoxyethylene alkyl ether) previously adjusted to a 20% aqueous solution. A monomer emulsion comprising 180.0 parts of a sulfate ester salt (hereinafter the same) and 194 parts of deionized water was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the obtained reaction liquid to room temperature, 5 parts of 25% ammonia water was added, 55% non-volatile content, pH 7.5, viscosity 350 mPa · s, particle diameter 270 nm, weight average molecular weight 90,000, Tg 0 ° C., SP value A 9.9 emulsion was obtained.

Production Example 2 (Production of Emulsion A)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, the dropping funnel comprises 544 parts of methyl methacrylate, 446 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, 5 parts of t-dodecyl mercaptan, 180.0 parts of Lebenol WZ previously adjusted to a 20% aqueous solution and 194 parts of deionized water. A monomer emulsion was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the obtained reaction liquid to room temperature, 5 parts of 25% aqueous ammonia was added, 55% non-volatile content, pH 7.5, viscosity 370 mPa · s, particle diameter 270 nm, weight average molecular weight 90,000, Tg 0 ° C., SP value An emulsion of 9.7 was obtained.

Production Example 3 (Production of Emulsion A)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, a monomer comprising 471 parts of styrene, 519 parts of butyl acrylate, 10 parts of acrylic acid, 5 parts of t-dodecyl mercaptan, 180.0 parts of Lebenol WZ previously adjusted to a 20% aqueous solution and 194 parts of deionized water in the dropping funnel. The emulsion was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the obtained reaction liquid to room temperature, 5 parts of 25% ammonia water was added, 55% non-volatile content, pH 7.1, viscosity 150 mPa · s, particle size 270 nm, weight average molecular weight 90,000, Tg 0 ° C., SP value An emulsion of 9.4 was obtained.

Production Example 4 (Production of Emulsion A)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, the dropping funnel was composed of 544 parts of styrene, 446 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, 5 parts of t-dodecyl mercaptan, 180.0 parts of Lebenol WZ previously adjusted to a 20% aqueous solution and 194 parts of deionized water. A mass emulsion was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the obtained reaction liquid to room temperature, 5 parts of 25% aqueous ammonia was added, 55% non-volatile content, pH 7.1, viscosity 160 mPa · s, particle diameter 270 nm, weight average molecular weight 90,000, Tg 0 ° C., SP value An emulsion of 9.1 was obtained.

Production Example 5 (Production of Emulsion B)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, a monomer emulsion comprising 960 parts of ethyl acrylate, 30 parts of trimethylolpropane trimethacrylate, 10 parts of acrylic acid, 180.0 parts of Lebenol WZ previously adjusted to a 20% aqueous solution and 194 parts of deionized water is added to the dropping funnel. Prepared. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the obtained reaction liquid to room temperature, 5 parts of 25% ammonia water was added, and the nonvolatile content was 55%, pH 7.1, viscosity 400 mPa · s, particle size 270 nm, Tg-20 ° C., SP value 10.2. An emulsion was obtained.

Production Example 6 (Production of Emulsion B)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, the dropping funnel comprises 424 parts of styrene, 536 parts of 2-ethylhexyl acrylate, 30 parts of trimethylolpropane trimethacrylate, 10 parts of acrylic acid, 180.0 parts of Lebenol WZ previously adjusted to a 20% aqueous solution, and 194 parts of deionized water. A monomer emulsion was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the resulting reaction liquid to room temperature, 5 parts of 25% aqueous ammonia was added, and the non-volatile content was 55%, pH 7.8, viscosity 200 mPa · s, particle size 270 nm, Tg-20 ° C., SP value 9.1. An emulsion was obtained.

Production Example 7 (Production of Emulsion B)
468.3 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 ° C. while stirring under a nitrogen gas stream. On the other hand, the dropping funnel is composed of 424 parts of styrene, 566 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, 5 parts of t-dodecyl mercaptan, 180.0 parts of Lebenol WZ previously adjusted to a 20% aqueous solution and 194 parts of deionized water. A mass emulsion was charged. Next, while maintaining the internal temperature of the polymerization vessel at 80 ° C., 8 parts of the monomer emulsion and 40 parts of a 5% potassium persulfate aqueous solution were added to initiate initial polymerization. After 20 minutes, the remaining monomer emulsion was uniformly added dropwise over 180 minutes while maintaining the inside of the reaction system at 80 ° C. The same temperature was maintained for 60 minutes after the completion of dropping. After cooling the obtained reaction liquid to room temperature, 5 parts of 25% ammonia water was added, 55% non-volatile content, pH 7.1, viscosity 180 mPa · s, particle size 270 nm, weight average molecular weight 60,000, Tg-20 ° C., An emulsion having an SP value of 9.1 was obtained.

Examples 1-6 and Comparative Examples 1-4
Emulsion A and Emulsion B (including commercial products) obtained in each of the above production examples were mixed in the types and blending amounts shown in Table 1 below, and stirred with a disper at 1000 rpm × 5 minutes to obtain a resin for heating and drying. It was.
Table 2 below summarizes the characteristics and the like of emulsion B.

<Preparation of thick film coating composition for heat drying>
The heat drying resins obtained in the above Examples and Comparative Examples were blended as follows to obtain a thick film coating composition for heat drying. Moreover, the coating-film surface state at the time of heat-drying was evaluated with the following test method. The results are shown in Table 1.
Resin for heat drying (solid content) 359 parts Calcium carbonate (NN # 200 ^{* 1} ) 620 parts Dispersant (Aquaric DL-40S ^{* 2} ) 6 parts Thickener (Acryset WR-650 ^{* 3} ) 4 parts Antifoaming agent (Nopco 8034L ^{* 4} ) 1 part Foaming agent (F-30 ^{* 5} ) 6 parts * 1: Nitto Flour Chemical 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: Anti-foaming agent manufactured by San Nopco (main component: hydrophobic silicone + mineral oil)
* 5: Matsumoto Yushi Co., Ltd. foaming agent

<Heat drying test (baking test)>
On the glass plate, the produced thick film coating composition for heating and drying was applied so as to have a coating size of 90 × 110 mm, a wet thickness of 5 mm, and a coating thickness of 6 mm (after drying). After that, vertical baking was performed at 150 ° C. for 30 minutes using a hot air dryer. The surface condition of the obtained dried coating film was evaluated according to the following criteria.
(Dry coating surface condition)
○: No abnormality △: Cracks on the coating surface or interface ×: Check that the shape of the coating is not maintained

As a result of the seizure test, Examples 1 to 6 using the emulsions in which the SP value difference between the polymer forming the polymer emulsion and the polymer forming the cross-linked polymer emulsion is 0.5 or more are all securable. (Heat drying property) was shown. In particular, in the case of Examples 1 to 4, there is no abnormality in the coating film after baking, and it shows excellent heat drying property in a thick film having a wet thickness of 5 mm and a coating thickness of 6 mm (film thickness after drying). It was found to be suitable as a film coating composition. Moreover, in Examples 1-4, it turned out that the compounding quantity of the emulsion B exists in a more preferable range, and is excellent by the heat drying property in a thick film compared with Examples 5-6 which are outside this range. .
Comparative Examples 1 and 2 using a crosslinked polymer emulsion having an SP value difference of less than 0.5, Comparative Example 3 using an uncrosslinked polymer emulsion even when the SP value difference is 0.5 or more, and Comparative Example 4 using only a polymer emulsion In both cases, even when the weight average molecular weight of the polymer emulsion is in a range suitable as a resin for heat drying, the heat drying property is inferior.
In the above examples, a polymer emulsion (base resin) having a weight average molecular weight suitable as a heat drying resin is used, and a polymer emulsion (base resin) having an SP value difference of 0.5 or more and a crosslinked polymer emulsion (blend resin) are used. As described above, the base resin and the blend resin are incompatible and each has a continuous structure. As a result, the effect of the base resin having a good drying property and the tough blend resin is effective. It is presumed that the drying property has been improved, and such an action mechanism is considered to be expressed in the same manner in the heat drying resin of the present invention.
Therefore, from the results of the above production examples and examples, the present invention can be applied in various technical forms of the present invention and in various forms disclosed in the present specification, and advantageous effects can be exhibited. I can say that.

Claims (3)

A resin for heat-drying which essentially comprises a polymer emulsion and a crosslinked polymer emulsion,
The polymer forming the polymer emulsion has a weight average molecular weight of 20,000 to 800,000,
The polymer for forming the crosslinked polymer emulsion has a solubility parameter value different from that of the polymer for forming the polymer emulsion by 0.5 or more. The resin for heat-drying according to claim 1, wherein the polymer forming the polymer emulsion has a glass transition temperature of -20 to 40 ° C. The heat drying according to claim 1 or 2, wherein the heat drying resin contains 10 to 100 parts by mass of a polymer that forms a crosslinked polymer emulsion with respect to 100 parts by mass of the polymer that forms the polymer emulsion. Resin.