JPS584940B2 - Baked-on soundproofing paint - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel baking-type soundproofing paint.

More specifically, styrene-butadiene rubber, rosin,
Baking type soundproofing that uses at least one selected from the group consisting of rosin derivatives and petroleum resins as a color vehicle and has excellent soundproofing properties, impact resistance, chipping resistance, etc., and does not sag on vertical surfaces or back surfaces when baked. Regarding paint.

In general, unlike other types of pollution, noise does not directly cause serious damage or harm to the human body.

However, since it causes insomnia, neurosis, etc., prevention measures have recently been attracting particular attention.

For example, soundproofing paints have been applied to noise sources such as vehicles, elevators, and refrigeration equipment.

Conventionally, soundproofing paints for such materials have been widely used, which include bituminous materials such as coal tar and asphalt, and fibrous materials such as asbestos.

However, there is a problem in that bituminous materials, asbestos, etc. used in this type of paint are carcinogenic, and an improvement has been desired.

Therefore, in order to solve the above-mentioned problems, various soundproofing paints using materials other than bituminous materials, such as synthetic resins, as a color vehicle have been proposed.

For example, soundproofing paints containing synthetic resin or synthetic rubber (Japanese Unexamined Patent Publication No. 52-51428) are known, but these are generally extremely poor in impact resistance, adhesion, etc. In particular, synthetic rubbers such as nitrile rubber and polybutadiene rubber are known. , those using depolymerized rubber have poor adhesion and are therefore almost impractical for use in vehicles such as automobiles, which require very harsh conditions.

As described above, no soundproofing paint has yet been obtained that has excellent performance in terms of adhesion and impact resistance against severe vibrations and shocks (particularly shocks at low temperatures).

On the other hand, soundproofing paints are often forced to dry to form a coating, and the temperature in this case varies considerably depending on line conditions, but is generally 80°C to 150°C.

During heating and drying, the viscosity of the paint film decreases temporarily due to humidification, and as a result, the wet paint film thickness, which is 3 to 5 layers thick, can cause defects such as sagging on vertical or back surfaces. there were.

As a solution to these problems, attempts have been made to improve the sag during baking by increasing the viscosity of the paint by adding thickeners and reducing the amount of solvent. If the coating temperature is increased, paint sprayability becomes difficult, and therefore this method has its limitations.

As described above, no soundproofing paint has been obtained that improves the back and vertical sagging of thick films during baking.

In view of the current situation as described above, the present invention not only has soundproofing properties, but also
The object of the present invention is to provide a baking-type soundproofing paint that has even better performance in terms of impact resistance, adhesion, chipping resistance, etc., and at the same time does not sag vertically or on the back surface during baking.

That is, the present invention provides (a) 30 to 90% by weight of solvent-soluble styrene-butadiene rubber obtained by a solution polymerization method; and (b) a compound selected from the group consisting of rosin, rosin derivatives, and petroleum resins. Color vehicle consisting of 10 to 70% by weight of at least one type...................................100
Parts by weight, ←) Filler・・・・・・・・・・・・1
0 to 500 parts by weight, (→ Vulcanizing agent...
...Relates to a baking-type soundproofing paint comprising a proportion of 0.5 to 10 parts by weight.

The styrene-butadiene rubber used in the present invention is a solvent-soluble styrene-butadiene rubber obtained by a generally commercially available solution polymerization method.

In particular, stereostyrene butadiene rubber produced by solution polymerization is preferred.

The stereostyrene-butadiene rubber includes a random copolymer or a block copolymer of styrene and butadiene.

Further, examples of the rosin used in the present invention include wood rosin, gum rosin, tall oil rosin, etc., and examples of the rosin derivative include rosin esters modified with maleic acid, phenol, etc.

Further, the petroleum resins used in the present invention include synthetic literpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and aliphatic cyclic hydrocarbon resins.

Each component of the rosin, rosin derivative, and petroleum resin can be used singly or as a mixture of two or more.

The soundproofing paint of the present invention comprises a solvent-soluble styrene-butadiene rubber obtained by the solution polymerization method as described above, rosin,
The main color vehicle is at least one selected from the group consisting of rosin derivatives and petroleum resins.

When mixing them, styrene butadiene rubber 30 to 9
0% by weight, preferably 40-80% by weight, and 10-70% by weight, preferably 20-60% by weight of at least one selected from the group consisting of rosin, rosin derivatives, and petroleum resins.

Furthermore, in another aspect of the present invention, the color vehicle 100
The soundproofing paint includes 5 to 40 parts by weight, preferably 7 to 35 parts by weight of epoxy ester resin.

By doing so, the solvent resistance of the coating film can be improved.

Examples of the epoxy ester resin include those obtained by esterifying a bisphenol type epoxy resin having an epoxy equivalent of about 300 to 2,500 with a fatty acid such as dehydrated castor oil, linseed oil, soybean oil, safflower oil, and tall oil.

The epoxy ester resins also include those modified with acrylic or urethane by conventional methods.

The mixing ratio of each component is determined in relation to the purpose of the present invention.

For example, if the amount of styrene-butadiene rubber mixed is less than the above range, impact resistance, soundproofing properties, etc. will decrease.

Further, the purpose of adding rosin and/or rosin derivatives is to improve the adhesion of the coating film, but if the amount added exceeds the above-mentioned amount, the elasticity of the coating film decreases and the impact resistance deteriorates.

Furthermore, petroleum resins are mixed and used within the above range in order to improve the water resistance, adhesion, alkali resistance, chipping resistance, etc. of the coating film.

Furthermore, epoxy ester resins are mixed and used within the above range in order to improve the solvent resistance, adhesion, etc. of the coating film.

In addition, when the rosin and/or rosin derivative and petroleum resin are mixed and used, the petroleum resin in the mixture is 80% by weight or less, particularly 50 to 75% by weight (the weight of the rosin and/or rosin derivative and petroleum resin). Ratio 1:1~
It is preferable to adjust to 3).

Further, as the vulcanizing agent used in the present invention, sulfur or an organic peroxide having a decomposition temperature (half-life of 1 minute) of 100 to 170°C, such as 1,1-bis(t-butylperoxy)
3,3.5-trimethylcyclohexane, n-butyl 4
, 4-bis(t-butylperoxy)valerate, ■,
1-di(1-butylperoxy)cyclohexane, caprylic peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxide
Examples include so-propyl carbonate.

The vulcanizing agent is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight (nonvolatile content) of the color vehicle.

If the amount of the vulcanizing agent is less than 0.5 parts by weight, there is no effect of preventing dripping, and if it exceeds 10 parts by weight, the film becomes hard and the impact resistance, chipping resistance, etc. are deteriorated, which is not preferable.

In the present invention, when sulfur is used as a vulcanizing agent, it is preferably 20 to 150% by weight based on the vulcanizing agent, preferably 50 to 150% by weight.
130% by weight of vulcanization accelerator is used.

As the vulcanization accelerator, all those commonly used in combination with sulfur can be used.

For example, diphenylquanidine, 2-mercaftobenzothiazole, dibenzothiazyl disulfide, 2-(
4'monomorpholinodithio)benzothiazole, N-cyclohexyl-2-benzothiazylsulfphenamide,
Organic accelerators such as tetramethylthiuram, monosulfide, tetramethylthiuram disulfide, or inorganic accelerators such as zinc white, zinc carbonate, magnesium oxide, stearic acid, oleic acid, lauric acid, etc.
Alternatively, fatty acids such as zinc stearate or derivatives thereof may be mentioned.

These may be used alone or as a mixture of two or more.

On the other hand, the fillers used in the present invention include, for example, plastic fibers, glass fibers, wollastonite, diatomaceous earth, wood flour, rice hull powder, cork powder, micro balloons, shirasu balloons, resin powders, and mica-like iron oxides. , tire powder, cotton powder, natural calcium silicate powder, asbestos powder, fibrous single crystal of insoluble anhydrite, etc.

These may be used alone or as a mixture of two or more.

In particular, it is preferable to use fibrous single crystals of insoluble anhydrite because they are less irritating to the skin and are therefore superior in the production and application work of paints.

The fibrous single crystal (II CaSO, ) is α-type gypsum (α-
Obtained by heating and stabilizing CaSO4.

The fibrous single crystal has a diameter (d) of 0.1 to 30μ, a length (4) of 10 to 5000μ, and a g/d of 20 to 200μ.
It is preferable that d is 0.5 to 6μ and l is 30 to 6μ.
400μ and t/d of 30 to 90 are preferred.

The filler is 10 to 500 parts by weight, preferably 30 to 400 parts by weight, based on 100 parts by weight (nonvolatile content) of the coloring agent.
Used in parts by weight.

If the amount of the filler is less than 10 parts by weight in the above ratio, the soundproofing effect will not be so great, and the coating film will tend to crack and blister during heating and drying.

Moreover, if more than 500 parts by weight is added, the rust prevention properties, impact resistance, film formability, chipping resistance, etc. of the coating film will be deteriorated, which is not preferable.

If necessary, ordinary coloring pigments, extender pigments, other synthetic resins, solvents, additives, etc. can be added to the baking-type soundproofing paint of the present invention.

The baking-type soundproofing paint of the present invention can be obtained by adding the coloring agent and filler, and if necessary, the solvent, etc., and stirring and mixing.

The soundproofing paint of the present invention thus obtained is applied onto the object by a conventional method such as brushing, spraying, dipping, or roller painting, and is baked at 80 to 150°C to form a film. It is said that

In the present invention, by using a coloring material that is a combination of at least one selected from styrene-butadiene rubber, rosin, rosin derivatives, and petroleum resins, excellent soundproofing properties, impact resistance, adhesion, chipping resistance, and water resistance are achieved. It has alkali resistance, etc., and can produce a coating that does not sag on vertical surfaces or back surfaces when baked, so it can be used, for example, as soundproofing paint on the bottom of cars, the back of stainless steel kitchen sinks, attics and walls of buildings. It can be used for a wide range of purposes, both domestic and industrial, such as the back side of materials, curtain walls, elevators, refrigeration equipment, and general vehicles.

The details of the present invention will be explained below with reference to Examples.

"Part" or "%" represents "part by weight" or "% by weight", respectively.

Example 1 50 parts of styrene-butadiene rubber obtained by solution polymerization [30% non-volatile solution of Tuffrene 1 (trade name, manufactured by Asahi Kasei Corporation) dissolved in xylol: styrene/butadiene = 416, Prosoc copolymer with a molecular weight of 70,000 to 100,000] Maleated rosin 5 [75% solution of non-volatile content obtained by dissolving Harima Tsuku R-80 (trade name, manufactured by Harima Kasei ■, in xylol)] Synthetic polyterbene resin 10 [70% solution of non-volatile content, prepared by dissolving brand name Quinton 1500 (manufactured by Nippon Zeon ■) in xylol] Talc 13.5 Fibrous single crystal of insoluble anhydrite C7=15 0-400μ, d2-6μt/d-
30-80] 20 peroxide [trade name: Perhexa 3M, manufactured by NOF ■ 1.5100 The above composition was stirred and mixed with a disper to obtain the soundproofing paint of the present invention.

The paint was applied by airless spray painting on a mild steel plate, and as a back sag removal test, immediately after painting, the paint was set with the surface facing down for 20 minutes, and then forced drying was performed at 150°C for 20 minutes to remove any sag. I saw sex.

For other tests, test pieces were prepared in the same manner, dried in the same manner, and then allowed to stand at room temperature for 24 hours.

The same procedure was carried out for the following Examples and Comparative Examples.

Example 2 Styrene butadiene rubber (same as Example 1) 50 parts Maleated rosin (same as Example 1) 5 Synthetic polyterbene resin (same as Example 1) 6.5 Epoxy ester resin 3.5 [Nippon Reichhold Co., Ltd. Product name: Betucosol P786, using dehydrated castor oil, non-volatile content: 50%] Talc 14.8 Natural calcium silicate powder 2o [Product name: Wallastonite F-D, manufactured by Interpace Co., Ltd. Peroxide 0.2 [Product name: Nivar B, manufactured by NOF ■ ] 100 Example 3 Styrene-butadiene rubber (same as Example 1) 50 parts Maleated rosin (same as Example 1) 10 Synthetic polyterbene resin (same as Example 1) 10 Talc
8 Natural calcium silicate powder (same as Example 2) 20 Nono-oxide [trade name Perbutyl 12 manufactured by NOF ■ 100 Example 4 Styrene-butadiene rubber (same as Example 1) 50 parts Maleated rosin (Example 1) ) 5 Synthetic polyterpene resin (same as Example 1) 10 Talc
14 Fibrous single crystal of insoluble anhydrite 20 (same as Example 1) Sulfur powder 0.5 [Reagent special grade manufactured by Wako Pure Chemical Industries Ltd.] Vulcanization accelerator 0.5 [Product name Accel DS manufactured by Kawaguchi Chemical Company Ltd.] 100 Example 5 Styrene-butadiene rubber (same as Example 1) 50 parts Maleated rosin (same as Example 1) 5 Synthetic polyterpene resin (same as Example 1) 10 parts
12 Natural calcium silicate (same as Example 2) 20 Sulfur powder (same as Example 4) 1.3 Vulcanization accelerator A1.0 [Product name: Accel DM manufactured by Kawaguchi Kagaku ■] Vulcanization accelerator BO. 7 [Product name: Accel D manufactured by Kawaguchi Kagaku ■] 100 Example 6 40 parts of styrene-butadiene rubber obtained by solution polymerization method [Product name: Solprene 411 manufactured by Asahi Kasei Corporation ■ 30% solution dissolved in xylol: Styrene/butadiene = 3 /7, block copolymer with a molecular weight of 240,000 to 250,000] maleated rosin (same as Example 1) 10 epoxy ester resin (
Same as Example 2) 10 Fibrous single crystal of insoluble anhydrite 30 [Product name: ONODA-GF manufactured by Onoda Cement ■: t2 30~120μ, d=0.5~
1.5μ, t/d=30~90] Kuruku
8 sulfur powder (same as Example 4) ■Vulcanization accelerator
1 [Product name: Accel CZ manufactured by Kawaguchi Kagaku ■] 100 Example 7 Styrene-butadiene rubber (same as Example 1) 50 parts Maleated rosin (same as Example 1) 10 Aliphatic cyclic hydrocarbon resin 15 [Arakawa Zaisan Co., Ltd. 70% solution of non-volatile content made by dissolving Alcon P85 manufactured by Kagaku ■ in xylol] Fibrous single crystal of insoluble anhydrite 15 parts [7=1
50-400μ, d2-6μ, t/d=30-80] Talc 9.4 Sulfur powder (same as Example 4) 0.3 Vulcanization accelerator (same as Example 4) 0.3 100 Implementation Example 8 Styrene-butadiene rubber (same as Example 1) 40 parts Synthetic polyterpene resin (same as Example 1) 20 Insoluble anhydrite fibrous single crystal 30 [=30-150μ, d
=1~2μ, t/d=20~80] Curc 7.8 Sulfur powder (same as Example 4) 1.2 Vulcanization accelerator (same as Example 4) 1100 Example 9 Styrene-butadiene rubber (Example Same as 1) 50 parts Rosin ester 10 [75% solution of Ester Gum H manufactured by Arakawa Hayashi Chemical Co., Ltd., dissolved in xylol] Aromatic hydrocarbon resin 15 [Non-volatile solution of Escorets 3102, manufactured by Esso Chemical Co., Ltd., dissolved in xylol 50% solution] Talc 8 wollastonite 15 sulfur powder (same as Example 4) ■Vulcanization accelerator (same as Example 4) 1100 Example 10 Styrene-butadiene rubber (same as Example 1) 50 parts Gum rosin 15 (Produced in China, xylene solution with a softening point of 70-75°C, oxidation of 165 or more, and non-volatile content of 15-75) Kuruku 13.5 Fibrous single crystal of insoluble anhydrite 20 (same as Example 1) Peroxide 1. 5 (same as Example 1) 100 The above composition was stirred and mixed and applied in the same manner as Example 1.
It was subjected to a comparative test.

Example 11 Styrene-butadiene rubber (same as Example 1) 50 parts Gum rosin (Same as Example 10) 5 Aliphatic cyclic hydrocarbon resin 10 (Same as Example 7) Kuruku 14.8 Natural calcium silicate (Example 1) 20 peroxide (same as Example 2) 0.2100 The above composition was stirred and mixed and applied in the same manner as Example 1.
It was subjected to a comparative test.

Example 12 Styrene butadiene rubber (same as Example 1) 50 parts Gum rosin (same as Example 10) 6 Aliphatic cyclic hydrocarbon resin 9 (same as Example 7) Talc 8 Natural calcium silicate powder (Example 2) ) 20 Epoxy ester resin (same as Example 2) 5 Peroxide (same as Example 3) 2100 The above compositions were stirred and mixed and applied in the same manner as Example 1.
It was subjected to a comparative test.

Comparative Example 1 Styrene-butadiene rubber (same as Example 1) 60 parts Asbestos powder 10 Talc
30100 Comparative Example 2 Asphalt (xylol 60% solution) 5 0
Part talc 20 Asbestos powder 30100 Comparative example 3 Styrene butadiene rubber (same as Example 1) 50 parts Maleated rosin (Same as Example 1) 5 Synthetic polyterpene resin (Same as Example 1) 10 parts
15 Natural calcium silicate powder (
Same as Example 2) 20 Comparative Example 4 Styrene-butadiene rubber (same as Example 1) 50 parts Rosin ester 10 [75% solution of Ester Gum H manufactured by Arakawa Forestry Chemical Co., Ltd., dissolved in xylol] Aliphatic cyclic carbonization Hydrogen resin 15 (Example 7
Talc 9.8 Natural calcium silicate powder (same as Example 2) 15 Sulfur powder (same as Example 4) 0.1 Vulcanization accelerator (same as Example 4) 0.1 100 Comparative example 5 Styrene-butadiene rubber (same as Example 1) 50 parts Maleated rosin (same as Example 1) 5 Synthetic polyterpene resin (same as Example 1) 10 Talc
11 Natural calcium silicate powder (
Same as Example 1) 20 sulfur powder (Same as Example 4)
3 Vulcanization accelerator (same as Example 4) 1
100 As is clear from the above comparative test results table, the baked-on soundproofing paint of the present invention not only has superior soundproofing properties compared to conventional soundproofing paints, but also has excellent adhesion, pitting resistance, and impact resistance. It is clear that it is significantly superior in all respects.

Claims (1)

[Claims] 1G) (a) 30 to 90% by weight of solvent-soluble styrene-butadiene rubber obtained by a solution polymerization method, and (b) a small amount selected from the group consisting of rosin, rosin derivatives, and petroleum resins. A color vehicle consisting of 10 to 70% by weight of each type...
100 parts by weight, (D) Filler・・・・・・・・・
...10 to 500 parts by weight, (/) vulcanizing agent...
・・・・・・・・・・・・Baking type soundproofing paint consisting of 0.5 to 10 parts by weight. 2. The baking type soundproofing paint according to claim 1, wherein the vulcanizing agent is sulfur or an organic peroxide. 3. The baking type soundproofing paint according to claim 1, wherein the filler is a fibrous single crystal of insoluble anhydrite. 4 The fibrous single crystal of the insoluble anhydrite has a diameter (d) of 0
．． The baking type soundproofing paint according to claim 3, having a length (C) of 1 to 30 μm, a length (C) of 10 to 5000 μm, and a ratio t1d of 20 to 200. 5 B) (a) 30 to 90% by weight of solvent-soluble styrene-butadiene rubber obtained by a solution polymerization method, and (b) at least one selected from the group consisting of rosin, rosin derivatives, and petroleum resins. Color vehicle consisting of 70% by weight...100
Parts by weight, (IO) filler...
・10 to 500 parts by weight, (c) vulcanizing agent...
...0.5 to 10 parts by weight, and (d) epoxy ester resin...5 to 40 parts by weight. 6. The baking type soundproofing paint according to claim 5, wherein the vulcanizing agent is sulfur or an organic peroxide. 7. The baking type soundproofing paint according to claim 5, wherein the filler is a fibrous single crystal of insoluble anhydrite. 8 The fibrous single crystal of the insoluble anhydrite has a diameter (d) of 0
．． The baking type soundproofing paint according to claim 7, which has a length (4) of 10 to 5000μ, and a ratio t/d of 20 to 200.