JP2003206382A - Copolymer emulsion for vibration-damping material or chipping-resistant material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer emulsion for a vibration-damping material or a chipping-resistant material which can give an aqueous vibration-damping material excellent in thermal dryability and vibration-damping properties or an aqueous chipping material excellent in thermal dryability and chipping properties. <P>SOLUTION: This copolymer emulsion for a vibration-damping material or a chipping-resistant material is prepared by copolymerizing a monomer mixture essentially containing an acrylic monomer. The monomer mixture contains less than 10 wt.% unsaturated monomer having a functional group and at least 32 wt.% ethylenically unsaturated alkyl carboxylate monomer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a copolymer emulsion for a vibration damping material or a chipping resistant material. Specifically, it relates to a copolymer emulsion for a vibration damping material or a chipping resistant material, which is preferably used as a constituent of a vibration damping composition.

[0002]

2. Description of the Related Art Damping materials are used to prevent vibrations and noises in various structures to maintain quietness, and are used under the floor of the interior of automobiles, railway cars, ships and aircraft. It may also be used for electrical equipment, building structures, construction equipment, etc. As such a damping material, for example, an asphalt sheet containing an inorganic powder has been used under the interior floor of an automobile, etc., but since it is necessary to heat-bond it, it is possible to improve workability and the like. It has been desired to study various vibration damping composition and polymers for forming vibration damping materials.

Japanese Unexamined Patent Publication No. 9-104842 discloses a water-based vibration-damping coating composition containing a specific amount of at least one color-developing agent selected from a synthetic resin emulsion and an asphalt emulsion, an inorganic filler and a synthetic resin powder. ing. JP-A-11-29737 discloses (a) an aliphatic conjugated diene monomer, (b) an ethylenically unsaturated carboxylic acid monomer, and (c) a monomer other than these monomers. Disclosed is a copolymer latex obtained by copolymerizing in the presence of α-methylstyrene dimer in a specific weight ratio, wherein the loss coefficient (tan δ) and the toluene insoluble content are specified. ing.

Japanese Patent Laid-Open No. 2000-178497 discloses that
Conjugated diene monomer (a), ethylenically unsaturated carboxylic acid amide monomer (b), ethylenically unsaturated carboxylic acid monomer (c), and ethylenically unsaturated monomer (d) other than the above Disclosed is a copolymer latex for a chipping resistant coating obtained by emulsion polymerization of a monomer mixture containing a specific amount of ## STR1 ## in the presence of an inorganic persulfate-based polymerization initiator.
Further, in JP-A-2000-178498, a conjugated diene monomer (a), an ethylenically unsaturated monomer having an epoxy group (b), an ethylenically unsaturated carboxylic acid alkyl ester monomer (c ), A copolymer latex for a vibration damping material obtained by emulsion polymerization of a monomer mixture containing the ethylenically unsaturated monomer (d) other than (b) and (c) in a specific weight ratio is disclosed. ing. Furthermore, JP-A-2000-17
8499 discloses a conjugated diene monomer (a), an epoxy group-containing ethylenically unsaturated monomer (b), an ethylenically unsaturated carboxylic acid amide monomer (c), (b) and ( Disclosed is a copolymer latex for vibration damping materials obtained by emulsion polymerization of a monomer mixture containing an ethylenically unsaturated monomer (d) other than c) in a specific weight ratio.

However, with these techniques, it has not been possible to obtain a damping material which achieves both excellent heat-drying properties and damping properties. That is, when a synthetic resin emulsion or an asphalt emulsion is used, the coating film is dried by heating to dry the surface and moisture in the undried coating film tends to evaporate, which causes blistering. There was room for improvement to improve sex. In addition, as the damping property, the loss factor (tan) of the steel sheet with a 2 mm thick asphalt sheet currently used is
δ) is about 0.1, and it is required to show a value higher than that. A copolymer latex formed from a conjugated diene monomer and other monomer. In the case of using, since the monomer unit formed of the conjugated diene-based monomer does not sufficiently exhibit the vibration damping property, there is room for improvement of the vibration damping property.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an aqueous damping material exhibiting excellent heat drying property and vibration damping property, and excellent heat drying property and chipping property. An object of the present invention is to provide a copolymer emulsion for a vibration damping material or an anti-chipping material, which gives a water-based chipping material that exhibits

[0007]

The inventors of the present invention have investigated various polymers for damping materials, and a copolymer emulsion for damping materials which gives an aqueous damping material is excellent in workability and the like. First of all, the monomer mixture forming the copolymer emulsion for damping material contains less than a specific amount of an unsaturated monomer having a functional group, and the ethylenic unsaturated carboxylic acid alkyl ester mono It was found that the heat-drying property becomes excellent and the vibration damping property is improved by containing the body in a specific amount or more, and it has been conceived that the above problems can be solved satisfactorily. Further, when the ethylenically unsaturated carboxylic acid monomer and the other ethylenically unsaturated monomer are contained in a specific weight ratio, excellent heat drying properties and vibration damping properties of the water-based vibration damping material can be more sufficiently exhibited. It was also found that the water-based chipping material can exhibit excellent heat-drying property and chipping property, and has reached the present invention.

That is, the present invention is a copolymer emulsion for a damping material or a chipping resistant material, which is obtained by copolymerizing a monomer mixture containing an acrylic monomer as an essential component. A damping material containing less than 10% by weight of an unsaturated monomer having a functional group and 32% by weight or more of an ethylenically unsaturated carboxylic acid alkyl ester monomer, based on the monomer mixture. Alternatively, it is a copolymer emulsion for chipping resistant materials. The present invention is described in detail below.

The copolymer emulsion for damping material or anti-chipping material of the present invention is obtained by copolymerizing a monomer mixture containing an acrylic monomer as an essential component. The above-mentioned copolymer emulsion for damping material or chipping resistant material is an aqueous emulsion in which water is a continuous phase and a copolymer containing an acrylic monomer as an essential component is dispersed therein. Usually, a damping material is formed by applying such a damping material or a damping material which requires a copolymer emulsion for anti-chipping material, and a chipping material is formed by applying the blending material. Will be done. The damping material and chipping material formed of the emulsion are also referred to as water-based damping material and water-based chipping material, respectively.

The above acrylic monomer means a (meth) acrylic acid derivative such as (meth) acrylic acid or (meth) acrylic acid ester. The content of the acrylic monomer in the monomer mixture is, for example, preferably 32% by weight or more based on the total monomer mixture. In such a monomer mixture, the content of the conjugated diene-based monomer is preferably 10% by weight or less based on the total monomer mixture, from the viewpoint of vibration damping property and chipping property. It is more preferably 5% by weight or less, and most preferably it does not contain a conjugated diene monomer.

In the present invention, the above-mentioned monomer mixture essentially comprises an unsaturated monomer having a functional group and an ethylenically unsaturated carboxylic acid alkyl ester monomer, and is based on the total monomer mixture. The unsaturated monomer having a functional group
The content is less than 0% by weight, and the content of ethylenically unsaturated carboxylic acid alkyl ester monomer is 32% by weight or more. When the content of the unsaturated monomer having a functional group is less than 10% by weight and the amount of the ethylenically unsaturated carboxylic acid alkyl ester monomer is less than 32% by weight, the damping material or the The vibration-damping property and the chipping property of the vibration-damping material formed from the vibration-damping material mixture that requires the copolymer emulsion for chipping materials and the chipping agent formed from the chipping material composition become insufficient. The functional group in the unsaturated monomer having a functional group may be any functional group that can be crosslinked when the copolymer emulsion for vibration damping materials or chipping resistant materials is obtained by copolymerization. By the action of the unsaturated monomer having a functional group, it is possible to improve the film forming property and the heat drying property of the copolymer emulsion for the vibration damping material or the chipping resistant material. The action of the ester monomer facilitates adjustment of Tg, physical properties, and the like of the copolymer emulsion for damping material or chipping resistant material. In the present invention, by appropriately setting the weight ratio of the unsaturated monomer having a functional group and the ethylenically unsaturated carboxylic acid alkyl ester monomer in the monomer mixture, these synergistic effects can be sufficiently achieved. The copolymer emulsion for vibration-damping materials or chipping-resistant materials that has been demonstrated exhibits excellent heat-drying properties and vibration-damping properties and chipping properties. More preferably, the unsaturated monomer having a functional group is 0.1 to 3.0% by weight, and the ethylenically unsaturated carboxylic acid alkyl ester monomer is 32% by weight or more. The upper limit of the weight ratio of the ethylenically unsaturated carboxylic acid alkyl ester monomer is 90% by weight.
The following is preferable. More preferably, it is 60% by weight or less. In addition, the above-mentioned weight ratio is 10
It is a weight ratio with respect to 0% by weight.

Examples of the functional group include an epoxy 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. 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 in one molecule.

Examples of the unsaturated monomer having a functional group include divinylbenzene, ethylene glycol di (meth) acrylate, N-methoxymethyl (meth) acrylamide, 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 Polyfunctional unsaturated monomers such as glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate; glycidyl (meth) acrylate, acrylic glycidyl ether, etc. Examples thereof include glycidyl group-containing unsaturated monomers. Among these, it is preferable to use an unsaturated monomer having two or more functional groups (polyfunctional unsaturated monomer). These may be used alone or in combination of two or more.

The ethylenically unsaturated carboxylic acid alkyl ester monomer is not particularly limited, and examples thereof include unsaturated monomers having the above-mentioned functional groups, methyl (meth) acrylate, ethyl (meth) acrylate and butyl. One or more of (meth) acrylates such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be mentioned.

In the present invention, the above-mentioned monomer mixture may also contain 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 99.9 to another copolymerizable ethylenically unsaturated monomer.
It preferably comprises 80% by weight. Dispersion of fillers such as inorganic powder in a vibration damping composition or a chipping composition containing a copolymer emulsion for a vibration damping material or a chipping resistant material by containing an ethylenically unsaturated carboxylic acid monomer. Therefore, the vibration damping property and the chipping property are further improved. Further, by containing other copolymerizable ethylenically unsaturated monomer, it becomes easy to adjust Tg, physical properties and the like of the copolymer emulsion for vibration damping materials or chipping resistant materials. In the monomer mixture, even if the ethylenically unsaturated carboxylic acid monomer is less than 0.1% by weight,
Even if it exceeds 20% by weight, the emulsion may not be stably copolymerized. In the vibration damping material or the copolymer emulsion for chipping resistant material of the present invention, due to the synergistic effect of the monomer units formed from these monomers, excellent heat-drying property and vibration damping property in the water-based vibration damping material are obtained. In addition, the water-based chipping material can exhibit more excellent heat drying property and chipping property. The above weight ratio is based on 100% by weight of the total monomer mixture.

The ethylenically unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate and monomethylmai. 1 or 2 or more types of unsaturated carboxylic acids or their derivatives such as ates and monoethyl myates.

The other copolymerizable ethylenically unsaturated monomer is not particularly limited, and examples thereof include the above-mentioned unsaturated monomer having a functional group and ethylenically unsaturated carboxylic acid alkyl ester monomer. In addition, one or more aromatic unsaturated monomers such as styrene may be used.

When the number-average molecular weight of the copolymer emulsion for damping material or chipping resistant material of the present invention is small, the composition of damping material which requires the copolymer emulsion for damping material or chipping resistant material of the present invention, In the chipping material composition, the affinity between the filler such as the inorganic powder and the damping material or the copolymer emulsion for chipping resistant material is improved, and the dispersibility is improved. Further, the glass transition point (Tg) is -50 to 40.
C. is preferred. If the Tg is less than -50 ° C or more than 40 ° C, the vibration damping property and the chipping property may not be sufficient. More preferably, -10 to 35 ° C
Is. The Tg of the copolymer emulsion for damping material or chipping resistant material can be calculated by the Tg of the homopolymer of each monomer forming the copolymer emulsion for damping material or chipping resistant material.

The above-mentioned copolymer emulsion for damping material or anti-chipping material has a gel fraction of 0 to 0 measured with a toluene solvent.
It is preferably 45% by weight. The gel fraction in the present invention is an index showing the solubility in a toluene solvent of a film formed from a copolymer emulsion for damping materials or chipping-resistant materials, and the higher the gel fraction is, the more soluble it is in a toluene solvent. Means less. The gel fraction reflects the molecular structure of the resin, and when the gel fraction of the vibration damping material or the copolymer emulsion for chipping resistant material of the present invention exceeds 45% by weight, the vibration damping composition or the chipping material is used. There is a possibility that sufficient vibration damping property and chipping property may not be exhibited when the composition is used. Further, the temperature dependence of the vibration damping property and the chipping property becomes large, and for example, the vibration damping property and the chipping property have a peak of the vibration damping property in a specific temperature region. In order to exhibit excellent vibration damping property and chipping property, it is preferably 5 to 45% by weight. More preferably, it is 0 to 30% by weight.

As a method of measuring the gel fraction, for example,
For example, use the toluene insoluble content measurement method described below.
It is preferable to measureMeasuring method of gel fraction (toluene insoluble matter) Release of copolymer emulsion for damping material or chipping resistant material
Pour it into a 0.2 cm thick mold on paper to obtain a thickness of 0.2
Make a film of cm. This film is 2 cm
(Vertical) x 2 cm (Horizontal) x 0.2 cm
Let's call it Rum. This test film was added to 100 ml of toluene.
Immerse at room temperature with a magnetic stirrer at 6 o'clock
Stir for a while. Then, filter with 100 mesh wire mesh,
The solid content of the liquid is calculated and the gel content is calculated.

The above-mentioned copolymer emulsion for damping material or chipping resistant material has a loss factor (t
It is preferable that an δ) is 0.15 or more. That is, a vibration damping composition was prepared using the copolymer emulsion for vibration damping materials or chipping resistant materials of the present invention, and the loss factor (tan δ) of the film formed from this vibration damping composition was 0.1.
It is preferably 5 or more. The damping property, that is, the loss coefficient correlates with the tan δ of the coating used, and the higher the tan δ, the higher the loss coefficient and the better the damping property. If the loss coefficient (tan δ) is less than 0.15, the water-based vibration damping material may not be able to exhibit excellent vibration damping properties. It is more preferably 0.16 or more, still more preferably 0.18 or more.

Loss factor for the above damping composition
The method for measuring (tan δ) is described below, for example.
Therefore, it is preferable to prepare and measure the vibration damping composition.
GoodComposition of damping material Copolymer emulsion for damping material or chipping resistant material 100 parts by weight Calcium carbonate: NN # 200 (trade name, manufactured by Nitto Koka Kogyo Co., Ltd.) 250 parts by weight Dispersant: Demol EP (trade name, manufactured by Kao Corporation) 1 part by weight Thickener: Acryset AT-2 (trade name, manufactured by Nippon Shokubai Co., Ltd.) 2 parts by weight Defoaming agent: Nopco 8034L (trade name, manufactured by San Nopco) 0.3 parts by weight

[0023]Measuring method of loss factor (tan δ) The above vibration damping composition was applied to a cation electrodeposition coated steel sheet (15 width x 2
50 length x 0.8 mm thickness) and flow into a 3 mm thick mold
Immersion and drying at 150 ° C for 30 minutes were used as test pieces. this
About test pieces Loss factor measurement system made by Ono Sokki Co., Ltd.
Measures the loss factor of the measurement environment at 25 ℃ using the cantilever method
To do.

The method for producing the copolymer emulsion for damping material or anti-chipping material of the present invention will be described below. The vibration-damping material or anti-chipping material copolymer emulsion of the present invention is formed by copolymerizing a monomer mixture containing an acrylic monomer as an essential component.As a method of copolymerizing the monomer mixture, For example, an emulsion polymerization method can be suitably applied. The mode of carrying out emulsion polymerization is not particularly limited, and for example, it can be carried out by appropriately adding a monomer mixture, a polymerization initiator and a surfactant to an aqueous medium and performing copolymerization. Further, a polymerization chain transfer agent or the like may be used for controlling the molecular weight.

As a method for copolymerizing the above-mentioned monomer mixture, for example, an emulsion polymerization method can be preferably applied. The mode of carrying out emulsion polymerization is not particularly limited, and for example, it can be carried out by appropriately adding a monomer mixture, a polymerization initiator and a surfactant to an aqueous medium and performing copolymerization. Further, a polymerization chain transfer agent or the like may be used for controlling the molecular weight.

The above-mentioned aqueous medium is not particularly limited, and examples thereof include one or a mixed solvent of water and a solvent capable of mixing with water, or a mixture of such a solvent with water as a main component. Examples of the mixed solvent include Among these, it is preferable to use water.

The above-mentioned polymerization initiator is not particularly limited,
For example, known water-soluble or oil-soluble initiators such as ammonium persulfate, potassium persulfate, hydrogen peroxide, butyl hydroperoxide and the like can be mentioned. Further, in order to accelerate emulsion polymerization, sodium bisulfite, L
-A redox initiator may be used using ascorbic acid or the like. These may be used alone or in combination of two or more.

The amount of the above-mentioned polymerization initiator to be used is not particularly limited and may be appropriately set according to the kind of the polymerization initiator. For example, with respect to 100 parts by weight of the total monomer mixture,
It is preferably 0.1 to 2 parts by weight. More preferably, it is 0.2 to 1 part by weight.

The surfactant is not particularly limited,
For example, any of anionic emulsifiers, nonionic emulsifiers and nonionic anionic emulsifiers can be used. Among these emulsifiers, it is preferable to use a nonionic emulsifier and a nonionic anionic emulsifier from the viewpoint of emulsion polymerization stability, and it is more preferable to use a nonionic emulsifier and a nonionic anionic emulsifier together. Examples of the anionic emulsifier include fatty acid soap, rosin acid soap,
Examples thereof include alkyl sulfonic acid soap, dialkyl aryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate and the like. As the nonionic emulsifier, for example, polyoxyethylene alkyl ether,
Examples thereof include polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, and oxyethyleneoxypropylene block copolymer. These surfactants may be used alone or in combination of two or more.

The amount of the above-mentioned surfactant used is not particularly limited and may be appropriately set depending on the type of the emulsifier. For example, with respect to 100 parts by weight of the total monomer mixture,
It is preferably 0.05 to 5.0 parts by weight. More preferably, it is 0.1 to 3.0 parts by weight.

The polymerization chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, ethylene bromide, etc .; mercaptocarboxylic acid alkyl esters such as mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercapto pyropionic acid tridecyl ester; mercapto Acetoxy methoxybutyl ester, mercaptopropionic acid methoxybutyl ester and other mercaptocarboxylic acid alkoxyalkyl esters; Octanoic acid 2-mercaptoethyl ester and other carboxylic acid compounds And mercaptoalkyl esters, 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 usually 0 to 1 part by weight, preferably 0 to 0.5 part by weight, based on 100 parts by weight of the total monomer mixture.

In the above emulsion polymerization, if necessary,
It may be carried out in the presence of a chelating agent such as sodium ethylenediaminetetraacetate, a dispersant such as sodium polyacrylate, and an inorganic salt. The addition method of the monomer mixture or the polymerization initiator, for example, a batch addition method, a continuous addition method,
A method such as a multi-stage addition method can be applied. Also, these addition methods may be combined appropriately.

The reaction conditions in the emulsion polymerization are as follows:
It may be appropriately set depending on the composition of the monomer mixture, the polymerization initiator used, and the like. The polymerization temperature is preferably, for example, 5 to 90 ° C. More preferably, it is 20 to 85 ° C. The polymerization time is preferably, for example, 3 to 8 hours. Further, the polymerization and the dropping are preferably performed with stirring.

In the above-mentioned production method, it is preferable that after the copolymer emulsion is produced by emulsion polymerization, the emulsion is neutralized with a neutralizing agent. This stabilizes the copolymer emulsion. The neutralizing agent is not particularly limited, for example, triethanolamine, dimethylethanolamine, diethylethanolamine,
Tertiary amines such as morpholine; aqueous ammonia; sodium hydroxide and the like can be used. These may be used alone or in combination of two or more. Among these,
It is preferable to use a volatile base that volatilizes when the coating film is heated, since the water resistance and the like of the coating film formed from the vibration damping composition and the chipping composition that require the copolymer emulsion are improved. It is more preferable to use an amine having a boiling point of 80 to 360 ° C., since the heat drying property is improved and the vibration damping property and the chipping property are improved. As such a neutralizing agent, for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine are suitable.

The amount of the above-mentioned neutralizing agent added is not particularly limited. For example, the acid value of the copolymer emulsion for damping materials or chipping resistant materials, that is, the acid group contained in the copolymer emulsion for damping materials or chipping resistant materials. It is preferable to add the base of the neutralizing agent in an amount of 0.6 to 1.4 equivalents relative to 1 equivalent. More preferably, it is 0.8 to 1.2 equivalents.

The copolymer emulsion for damping material or anti-chipping material of the present invention can constitute a damping material composition or a chipping material composition, if necessary, together with additives, solvents and the like. Such a vibration damping composition or a chipping composition containing the damping emulsion or the copolymer emulsion for a chipping resistant material of the present invention is one of the preferred embodiments of the present invention, and has excellent heat-drying property. It is possible to form a water-based vibration damping material or a water-based chipping material by exhibiting the vibration damping property or the chipping property. Further, the copolymer emulsion for damping material or anti-chipping material of the present invention is suitable for both applications of damping material and chipping material, but particularly good performance as damping material and suitable for damping material. Is. A damping material formed from such a damping material composition or a chipping material formed from a chipping material composition, that is, a damping material formed by essentially using the damping material of the present invention or a copolymer emulsion for a chipping resistant material. Material or tipping material is one of the preferred embodiments of the present invention.

The amount of the copolymer emulsion for damping material or chipping resistant material in the damping material mixture that will form the above damping material is, for example, 100% by weight of the solid content of the damping material. On the other hand, it is preferable that the solid content of the copolymer emulsion for damping material or chipping resistant material is 30 to 60% by weight. The solid content concentration of the vibration damping composition is preferably, for example, 10 to 40% by weight based on 100% by weight of the vibration damping composition.

Examples of the above-mentioned additives include fillers, colorants, preservatives, dispersants, thickeners, thixotropic agents, antifreezing agents,
Examples thereof include pH adjusters, defoaming agents, wetting agents, rust preventives, adhesion promoters and the like. These may be used alone or 2
You may use together 1 or more types. Among these, it is preferable to include a filler.

The filler is not particularly limited, and examples thereof include inorganic fillers such as calcium carbonate, kaolin, silica, talc, barium sulfate, alumina, iron oxide, titanium oxide and glass talk; glass flakes, mica, etc. Scale-like inorganic fillers: fibrous inorganic fillers such as metal oxide whiskers and glass fibers can be mentioned.

The compounding amount of the filler in the vibration damping composition is, for example, 50 to 4 with respect to 100 parts by weight of the solid content of the copolymer emulsion for the vibration damping material or the chipping resistant material.
It is preferably set to 00 parts by weight. More preferably 1
It is from 00 to 350 parts by weight.

The solvent is not particularly limited as long as the effects of the present invention are exhibited, and one kind or two or more kinds can be used. Further, the amount of the solvent blended may be appropriately set, for example, so that the solid content concentration of the damping material blend falls within the above range.

It is preferable that the above-mentioned vibration damping composition also contains a polyvalent metal compound together with a copolymer emulsion for a vibration damping material or a chipping resistant material. This can improve the stability, dispersibility, heat-drying property of the vibration damping composition and the vibration damping property of the vibration damping material formed from the vibration damping composition. The polyvalent metal compound is not particularly limited, for example, zinc oxide,
Examples thereof include zinc chloride and zinc sulfate, and one type or two or more types can be used. Of these, zinc oxide is preferably used in the present invention.

The form of the polyvalent metal compound is not particularly limited and, for example, a powder, an aqueous dispersion or an emulsion dispersion can be used. Among these, since it is possible to improve the dispersibility of the vibration damping composition, it is preferable to use it in the form of an aqueous dispersion or an emulsion dispersion. More preferably, it is an emulsified dispersion. The amount of the polyvalent metal compound used is, for example, 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the solid content of the copolymer emulsion for damping material or chipping resistant material. Is preferred. More preferably,
It is 0.05 to 3.5 parts by weight.

The compounding amount of the damping material or the copolymer emulsion for chipping resistant material in the chipping material composition which forms the above tipping material is, for example, based on 100% by weight of the solid content of the chipping material composition. The solid content of the copolymer emulsion for damping material or chipping resistant material is 30
It is preferable to set the content to ˜60% by weight. Also,
The solid content concentration of the tipping material mixture is preferably, for example, 10 to 40% by weight based on 100% by weight of the tipping material composition.

The above-mentioned additive is not particularly limited, and the same ones as mentioned above can be mentioned, and it is preferable to include a filler. The amount of the filler in the chipping material mixture is, for example, 5 with respect to 100 parts by weight of the solid content of the copolymer emulsion for the vibration damping material or the chipping resistant material.
It is preferably from 0 to 400 parts by weight. More preferably, it is 100 to 350 parts by weight.

It is preferable that the above-mentioned tipping material composition also contains a polyvalent metal compound together with a copolymer emulsion for a vibration damping material or a chipping resistant material. This can improve the stability, dispersibility, heat-drying property of the chipping material mixture, and the chipping property of the chipping material formed from the chipping material composition. Examples of the polyvalent metal compound include the same ones as described above, and zinc oxide is preferably used. The form of the polyvalent metal compound is also the same as described above, and it is preferable to use it in the form of an aqueous dispersion or an emulsion dispersion because it improves the dispersibility of the tipping material formulation. More preferably, it is an emulsified dispersion. Also,
The amount used is preferably such that the polyvalent metal compound is 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the solid content of the copolymer emulsion for damping material or chipping resistant material. . More preferably 0.05 to 3.5
Parts by weight.

The solvent is not particularly limited as long as the effects of the present invention are exhibited, and one kind or two or more kinds can be used. Further, the amount of the solvent blended may be appropriately set, for example, so that the solid content concentration of the damping material blend falls within the above range.

The vibration-damping material mixture or chipping material composition that forms the above-mentioned vibration-damping material or chipping material comprises a copolymer emulsion for vibration-damping material or chipping-resistant material, and the above-mentioned additives and solvents. It can be manufactured by mixing. The device used for mixing is not particularly limited, and examples thereof include a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver, and the like.

The above-mentioned vibration damping composition or chipping composition is applied to a base material and dried to form a film which becomes the vibration damping material or the chipping material. The base material is not particularly limited. As a method of applying the vibration damping composition or the chipping composition to the substrate, for example, a brush, a spatula, an air spray, an airless spray, a mortar gun, a resin gun or the like can be used.

The application amount of the above-mentioned vibration damping composition or chipping material formulation may be set depending on the application and desired performance. For example, the vibration damping composition is applied to form the vibration damping material. In some cases, the film thickness when dried is 0.5 to
The thickness is preferably 5.0 mm, more preferably 1.5 to 4.5 mm. Further, when the tipping material composition is applied to form the tipping material, it is preferable that the thickness of the coating film when dried is 0.5 to 5.0 mm, and more preferably 1. 5-
It is 4.5 mm.

The conditions for applying the above-mentioned vibration damping composition or chipping material composition and then drying to form a film are as follows:
For example, it may be dried by heating or may be dried at room temperature,
From the viewpoint of efficiency, it is preferable to heat-dry, and the present invention is preferable because it has excellent heat-drying property. The heating and drying temperature is preferably 80 to 210 ° C., for example, when a vibration damping material is formed. More preferably, it is 110-160 degreeC. Moreover, when forming a chipping material, it is preferable to set it as 80-210 degreeC. More preferably, it is 110-160 degreeC.

The application of the vibration damping composition containing the vibration damping material or the copolymer emulsion for chipping resistant material of the present invention is not particularly limited, and it is possible to exhibit excellent heat-drying property and vibration damping property. Therefore, for example, in addition to under the floor of an automobile, railway vehicles, ships, aircraft, electrical equipment, building structures,
It can be suitably applied to construction equipment and the like. Further, since the chipping material composition that requires the vibration damping material or the copolymer emulsion for chipping resistant material of the present invention can exhibit excellent heat-drying property and chipping property, it can be used for automobile exteriors, automobile parts, and home appliances. It can be suitably applied to machines, machines and the like.

[0053]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" is
"Parts by weight" and "%" mean "% by weight".

Example 1 Deionized water was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 127.1 parts of methyl methacrylate and 25 parts of styrene were added to the dropping funnel.
3.7 parts, 2-ethylhexyl acrylate 147.1
Parts, 5.4 parts of divinylbenzene, 5.4 parts of acrylic acid,
53.8 parts of Nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Chemical Industry Co., Ltd.) adjusted to a 25% aqueous solution in advance, Hitenol N-08 (trade name, polyoxyethylene alkyl ether) adjusted to a 20% aqueous solution Sulfate ester salt: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 21.5
And a monomer emulsion consisting of 129.3 parts of deionized water. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 5% potassium persulfate aqueous solution 53.
9 parts and 40 parts of a 2% sodium hydrogen sulfite aqueous solution were uniformly added dropwise over 3 hours. After completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 5.1 parts of 25% ammonia water was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The obtained aqueous resin (copolymer emulsion) had a nonvolatile content of 55.1%, a pH of 8.7 and a viscosity of 480 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Example 2 A separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with deionized water 17
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 129.8 parts of methyl methacrylate and 25 parts of styrene were added to the dropping funnel.
3.7 parts, 2-ethylhexyl acrylate 147.1
Part, trimethylolpropane trimethacrylate 2.7
Part, acrylic acid 5.4 parts, nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Kasei Co., Ltd.) adjusted to a 25% aqueous solution in advance, 53.8 parts, Hitenol N-08 adjusted to a 20% aqueous solution. (Commercial name, sulfate salt of polyoxyethylene alkyl ether: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) A monomer emulsion consisting of 21.5 parts and 129.3 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 5.1 parts of 25% ammonia water was added. After cooling the emulsions, 10
It was filtered through a 0-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The obtained water-based resin (copolymer emulsion) has a nonvolatile content of 55.0%, a pH of 9.2, and a viscosity of 840 mPa.
It was s. Table 1 shows the monomer composition of the above monomer emulsion.

Example 3 Deionized water was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 127.1 parts of methyl methacrylate and 25 parts of styrene were added to the dropping funnel.
3.9 parts, 2-ethylhexyl acrylate 147.1
Parts, 5.4 parts of divinylbenzene, 5.4 parts of acrylic acid,
53.8 parts of Nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Chemical Industry Co., Ltd.) adjusted to a 25% aqueous solution in advance, Hitenol N-08 (trade name, polyoxyethylene alkyl ether) adjusted to a 20% aqueous solution Sulfate ester salt: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 21.5
And a monomer emulsion consisting of 129.3 parts of deionized water. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 5% potassium persulfate aqueous solution 53.
9 parts and 40 parts of a 2% sodium hydrogen sulfite aqueous solution were uniformly added dropwise over 3 hours. After completion of the dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 6.7 parts of dimethylethanolamine was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The nonvolatile content of the obtained aqueous resin (copolymer emulsion) was 54.6%, pH
Was 9.0 and the viscosity was 210 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Example 4 Deionized water was added to a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 129.8 parts of methyl methacrylate and 25 parts of styrene were added to the dropping funnel.
3.9 parts, 2-ethylhexyl acrylate 147.1
Part, trimethylolpropane trimethacrylate 2.7
Part, acrylic acid 5.4 parts, nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Kasei Co., Ltd.) adjusted to a 25% aqueous solution in advance, 53.8 parts, Hitenol N-08 adjusted to a 20% aqueous solution. (Commercial name, sulfate salt of polyoxyethylene alkyl ether: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) A monomer emulsion consisting of 21.5 parts and 129.3 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After the completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 6.7 parts of 25% dimethylethanolamine was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The obtained water-based resin (copolymer emulsion) has a nonvolatile content of 54.7%, a pH of 9.0, and a viscosity of 3
It was 50 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Example 5 A separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with deionized water 17
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 326.8 parts of styrene, 203.8 parts of 2-ethylhexyl acrylate, 2.7 parts of trimethylolpropane trimethacrylate, 5.4 parts of acrylic acid, 1.1 parts of t-dodecyl mercaptan, and a 25% aqueous solution were previously added to the dropping funnel. Nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Chemical Industries, Ltd.) adjusted to 53.8 parts, Hitenol N-08 adjusted to a 20% aqueous solution (trade name, sulfate salt of polyoxyethylene alkyl ether) (Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 21.5 parts and 129.3 parts of deionized water were charged. Next, while maintaining the internal temperature of the separable flask at 70 ° C.,
It dripped uniformly over time. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After the completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 6.7 parts of 25% dimethylethanolamine was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. Obtained aqueous resin (copolymer emulsion)
Has a nonvolatile content of 55.2%, a pH of 9.1 and a viscosity of 200.
It was mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Example 6 A separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introducing tube and a dropping funnel was charged with deionized water 17
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 326.8 parts of styrene, 203.8 parts of 2-ethylhexyl acrylate, 2.7 parts of trimethylolpropane trimethacrylate, 5.4 parts of acrylic acid, 1.1 parts of t-dodecyl mercaptan, and a 25% aqueous solution were previously added to the dropping funnel. Nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Chemical Industries, Ltd.) adjusted to 53.8 parts, Hitenol N-08 adjusted to a 20% aqueous solution (trade name, sulfate salt of polyoxyethylene alkyl ether) (Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 21.5 parts and 129.3 parts of deionized water were charged. Next, while maintaining the internal temperature of the separable flask at 70 ° C.,
It dripped uniformly over time. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After the completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 6.7 parts of 25% dimethylethanolamine was added. Later AZO-5
0 (Zinc oxide dispersion, 50% zinc oxide content: Nippon Shokubai Co., Ltd.) 30.5 parts was added and stirred for 30 minutes. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The resulting aqueous resin (copolymer emulsion) had a nonvolatile content of 55.1%, a pH of 8.9 and a viscosity of 180 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Comparative Example 1 Deionized water 17 was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 386.4 parts of styrene, 147.1 parts of 2-ethylhexyl acrylate, 5.4 parts of acrylic acid and nonipol 200 (trade name, polyoxyethylene phenyl ether: Sanyo Chemical Industries Co., Ltd.) previously adjusted to a 25% aqueous solution were added to the dropping funnel. Manufactured) 53.
8 parts, Hitenol N-08 adjusted to 20% aqueous solution
(Commercial name, sulfate salt of polyoxyethylene alkyl ether: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) A monomer emulsion consisting of 21.5 parts and 129.3 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After the completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 6.7 parts of 25% dimethylethanolamine was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The resulting aqueous resin (copolymer emulsion) had a nonvolatile content of 55.1%, a pH of 8.9 and a viscosity of 110 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Comparative Example 2 Deionized water 17 was added to a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 375.6 parts of styrene, 147.1 parts of 2-ethylhexyl acrylate, 10.8 parts of divinylbenzene, 5.4 parts of acrylic acid were added to the dropping funnel, and Nonipol 200 (trade name, polyoxyethylene) previously adjusted to a 25% aqueous solution. Phenyl ether: Sanyo Chemical Industry Co., Ltd.) 53.8 parts, Hitenol N-08 adjusted to a 20% aqueous solution (trade name, polyoxyethylene alkyl ether sulfate ester salt: Daiichi Kogyo Seiyaku Co., Ltd.) 21.5 parts And a monomer emulsion consisting of 129.3 parts of deionized water. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After dropping, 7
After aging at 6 ° C for 3 hours, the mixture was cooled and 6.7 parts of 25% dimethylethanolamine was added. After that, 30.5 parts of AZO-50 (dispersion of zinc oxide, containing 50% zinc oxide: manufactured by Nippon Shokubai Co., Ltd.) was added and stirred for 30 minutes. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The resulting water-based resin (copolymer emulsion) has a nonvolatile content of 55.3%, a pH of 9.3, and a viscosity of 1
It was 70 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

Comparative Example 3 Deionized water 17 was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
0.5 parts were charged. Then, the internal temperature was raised to 70 ° C. while stirring under a nitrogen gas stream. On the other hand, 371.8 parts of styrene, butyl acrylate 161.
7 parts, acrylic acid 5.4 parts, nonipol 200 (trade name, polyoxyethylene phenyl ether: manufactured by Sanyo Kasei Co., Ltd.) adjusted in advance to a 25% aqueous solution 53.8 parts, 20%
21.5 parts of Hitenol N-08 (trade name, sulfate salt of polyoxyethylene alkyl ether: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 129.3 parts of deionized water adjusted to an aqueous solution
A monomer emulsion consisting of parts was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 70 ° C. At this time, 53.9 parts of a 5% aqueous potassium persulfate solution and 40 parts of a 2% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 3 hours. After the completion of dropping, the mixture was aged at 76 ° C. for 3 hours, cooled, and 6.7 parts of 25% dimethylethanolamine was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. As a result, an aqueous resin (copolymer emulsion) was obtained. The obtained water-based resin (copolymer emulsion) has a nonvolatile content of 55.2%, a pH of 8.8, and a viscosity of 1
It was 90 mPa · s. Table 1 shows the monomer composition of the above monomer emulsion.

The copolymer emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to the following evaluation tests. The results are shown in Table 1. (1) Gel Fraction (Toluene Insoluble Content) The copolymer emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were poured into a mold having a thickness of 0.2 cm on a release paper, and the thickness was 0. A 0.2 cm film was made.
This film is 2cm (length) x 2cm (width) x 0.2c
The test film was cut into m. This test film was immersed in 100 ml of toluene and stirred at room temperature with a magnetic stirrer for 6 hours. Then, the mixture was filtered through a 100-mesh wire net, the solid content of the filtrate was determined, and the gel content was calculated.

(2) Loss Coefficient The copolymer emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were blended as follows, and the vibration damping property was confirmed as a vibration damping composition. (Composition of vibration damping compound) Acrylic copolymer emulsion 100 parts Calcium carbonate: NN # 200 (trade name, manufactured by Nitto Koka Kogyo Co., Ltd.) 250 parts Dispersant: Demol EP (trade name, manufactured by Kao) 1 part Thickening Agent: Acryset AT-2 (trade name, manufactured by Nippon Shokubai Co., Ltd.) 2 parts Defoaming agent: Nopco 8034L (trade name, manufactured by San Nopco Co.) 0.3 part The above damping composition was subjected to cation electrodeposition coated steel sheet (15). Width x 2
(50 length × 0.8 mm thickness), it was poured into a 3 mm thick mold and dried at 150 ° C. for 30 minutes to obtain a test piece. About this test piece, loss factor measurement system made by Ono Sokki Co., Ltd.
The cantilever method was used to measure the loss coefficient in a measurement environment of 25 ° C. to evaluate the vibration damping property. That is, the larger the value of the loss coefficient, the better the vibration damping property.

(3) Evaluation of chipping resistance The copolymer emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were blended as described below to obtain a chipping material blend. The following physical properties were confirmed from this tipping material mixture. (Composition of a chipping material compound) Acrylic copolymer emulsion 100 parts Calcium carbonate: NN # 200 (trade name, manufactured by Nitto Koka Kogyo Co., Ltd.) 100 parts Dispersant: Demol EP (trade name, manufactured by Kao Corporation) 1 part thickener : Acryset AT-2 (trade name, manufactured by Nippon Shokubai Co., Ltd.) 2 parts antifoaming agent: Nopco 8034L (trade name, manufactured by San Nopco Co.) 0.3 part Coated product prepared on a cationic electrodeposition coated plate Then
It dried at 150 degreeC for 30 minutes using the hot air dryer. The amount of coating was adjusted on the test plate so that the dry film thickness of this composition was 1.0 mm. For the measurement of chipping property, the dry coating film on the test plate was set up at an angle of 60 degrees with respect to the horizontal plane, and then a polyvinyl chloride pipe (inside diameter 2 cm) having a height of 2 m was set up on the dry coating film. Then, through the pipe, an M4 nut was continuously dropped from a height of 2 m onto the dry coating film surface, and the total weight of the nut dropped until the base of the test plate was exposed was measured. The total weight was expressed as chipping strength (Kg), and the chipping resistance was evaluated according to its size.

[0066]

[Table 1]

Table 1 will be described below. The emulsion composition is a monomer composition of the monomer emulsion used for producing the copolymer emulsion.

[0068]

Since the copolymer emulsion for damping material or chipping resistant material of the present invention has the above-mentioned constitution,
It can be preferably used as a constituent of a vibration damping composition. In addition, such a vibration damping material or a vibration damping composition that requires a copolymer emulsion for chipping resistant materials exhibits excellent heat-drying property and vibration damping property to form a water-based vibration damping material. Therefore, in addition to under the floor of automobiles, railway vehicles, ships, aircraft, electrical equipment, building structures,
It can be applied to construction equipment and the like. Furthermore,
Such a damping material or a chipping material formulation, which essentially requires a copolymer emulsion for chipping resistant materials, exhibits excellent drying properties and chipping properties, and can form a chipping material, so that the automobile exterior, It can be suitably applied to automobile parts, home appliances, machines and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 3J048 AA01 BA02 BA17 BD04 EA38                 4J002 BG051 GL00 HA07                 4J100 AB16P AJ01Q AJ02Q AJ08Q                       AJ09Q AL03P AL04P AL08P                       AL36Q AL62P AL80P AM15P                       BC04P EA07 FA20 JA67

Claims (2)

[Claims] 1. A copolymer emulsion for a damping material or a chipping resistant material, which is obtained by copolymerizing a monomer mixture containing an acrylic monomer as an essential component, wherein the monomer mixture comprises all monomers. A mixture containing less than 10% by weight of an unsaturated monomer having a functional group and 32% by weight or more of an ethylenically unsaturated carboxylic acid alkyl ester monomer with respect to the mixture. Copolymer emulsion for vibration and chipping resistant materials. 2. The monomer mixture comprises 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 99.9 to 80% by weight of another copolymerizable ethylenically unsaturated monomer. The copolymer emulsion for a vibration damping material or an anti-chipping material according to claim 1, characterized in that it comprises.