JPH0572872B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a laminate, and more specifically, it has excellent soundproofing properties, vibration proofing properties, etc., and is suitable for building materials such as flooring materials, wall materials, ceiling materials, and other structural materials. Regarding available laminates. [Prior Art] Materials mainly used as building materials, such as flooring materials, wall materials, ceiling materials, and other structural materials are required to have soundproofing and vibrationproofing properties that block various noises and vibrations as much as possible. Ru. Conventionally, such a material is a laminate in which the middle layer is an elastic body obtained by blending a polymerizable unsaturated compound such as methacrylic acid with a rubber such as an isobutylene-isoprene copolymer, and both outer layers are formed as a flexible plate. is known (see Japanese Unexamined Patent Application Publication No. 1983-7045). Although this laminate has the characteristic of effectively damping low-frequency vibrations, it has not yet reached a fully satisfactory level in soundproofing and vibrationproofing. [Problems to be Solved by the Invention] The present invention has significantly improved soundproofing properties and vibrationproofing properties, and can be suitably used as building materials such as flooring materials, wall materials, ceiling materials, and other structural materials. The purpose of this invention is to provide a practically excellent laminate. [Means for Solving the Problems] As a result of extensive research to solve the above problems, the present inventors have developed a specific liquid polymer obtained from a specific liquid polymer, a polyisocyanate compound, and solid rubber chips. The present inventors have discovered that a laminate having a layer of cured composition is extremely effective in achieving the object of the present invention, and have completed the present invention based on this knowledge. That is, the present invention provides a laminate in which a cured layer of a liquid polymer composition consisting of a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and solid rubber chips is formed on a substrate surface. As the hydroxyl group-containing liquid diene polymer,
A number average molecular weight of 300 to 25,000, preferably 500, having a hydroxyl group inside the molecular chain and/or at the end of the molecular chain.
~10,000 liquid diene-based polymers can be used. Here, the content of hydroxyl groups is usually 0.1 to 10meq/g,
Preferably it is 0.3 to 7meq/g. These liquid diene polymers have a carbon number of 4
-12 diene polymers, diene copolymers, and copolymers of these diene monomers with α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. Specifically, butadiene homopolymer,
Isoprene homopolymer, butadiene-styrene copolymer, butadiene isoprene 9 copolymer, butadiene-acrylonitrile copolymer,
Examples include butadiene-2-ethylhexyl acrylate copolymer and butadiene-n-octadecyl acrylate copolymer.
These liquid diene polymers can be produced, for example, by subjecting a conjugated diene monomer to a heating reaction in the presence of hydrogen peroxide in a liquid reaction medium. The polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has an isocyanate group reactive with the hydroxyl group of the hydroxyl group-containing liquid diene polymer. Examples of such polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic compounds, such as:
Trirediisocyanate, hexamethylene diisocyanate, diphenylmetadiisocyanate (MDI), liquid modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene -2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction products, etc.
Particularly preferred are MDI, liquid modified diphenylmethane diisocyanate, tolylene diisocyanate, and the like. As the solid rubber chips, chips of natural rubber, synthetic rubber, or a mixture or composition thereof can be used. Examples of this synthetic rubber include polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber, polychloroprene rubber (CR), polystyrene-butadiene rubber (SBR), polyacronitrile-butadiene rubber (NBR), and polyisobutylene rubber. -Isoprene rubber (IIR), ethylene-propylene rubber (EPR), ethylene-propylene rubber-diene rubber (EPT)
etc. can be mentioned. The shape of these solid rubber chips is not particularly limited and can be any shape such as spherical, elliptical, cubic, rectangular parallelepiped, cylindrical, linear, scaly, etc., and the size is usually the average diameter of the particles. 0.3 to 15 mm, preferably 0.5 to 10 mm can be used. If this average diameter is less than 0.3, the flexibility of the product may decrease, while if it exceeds 15 mm, the surface may become uneven when the composition is used, resulting in poor appearance and poor adhesion. The solid rubber chips having an average diameter within the above range can be suitably used. The liquid polymer composition can be prepared by blending the hydroxyl group-containing liquid diene polymer, the polyisocyanate compound, and the solid rubber chips in a predetermined ratio, but if necessary, the above components may be added. In addition, reinforcing agents, fillers, viscosity modifiers,
plasticizer, tackifier, adhesion promoter, curing accelerator,
It is desirable to prepare the composition by appropriately blending various additives such as anti-aging agents, antifoaming agents, aggregates, and solvents in appropriate amounts. The blending ratio of the hydroxyl group-containing liquid diene polymer and the polyisocyanate compound is such that the ratio of isocyanate groups (NCO) of the polyisocyanate compound to hydroxyl groups (OH) of the acid group-containing liquid diene polymer (NCO/OH) is , expressed as a molar ratio, is usually 0.2 to 25, preferably 0.5 to 15. If this blending ratio is outside the above range, curing becomes difficult, which is not preferable. The blending ratio of the solid rubber chips is usually 10 to 1000 parts by weight, preferably 30 to 1000 parts by weight, per 100 parts by weight of the hydroxyl group-containing diene polymer.
A suitable amount is 800 parts by weight. If the blending ratio of solid rubber chips is less than 10 parts by weight, flexibility may decrease, while if it exceeds 1000 parts by weight, adhesiveness may decrease. Suitable examples of the reinforcing agent include polyol compounds and polyamine compounds. As this polyol compound, any of primary polyols, secondary polyols, tertiary polyols, or mixtures thereof can be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3
-butanediol, 1,2-pentanediol,
2,3-pentanediol, 2,5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, glycerin, N,N'-bis-2-hydroxypropylaniline, Low molecular weight polyols containing a hydroxyl group bonded to at least one secondary carbon, such as N,N'-bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A, and the like. Furthermore, as this polyol compound, ethylene glycol, 1,3-propylene glycol, 1,
4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. can also be used. Among these polyol compounds, those having a molecular weight of 50 to 500 can be preferably used, and diols are usually preferably used, but triols,
Tetraol can also be used as appropriate. The polyamine compound may be any of diamine, triamine, tetraamine, etc.
Furthermore, primary polyamines, secondary polyamines,
Any tertiary polyamine can be used. Examples of the polyamine compound include aliphatic amines such as hexamethylene diamine, 3,3
- Dimethyl, alicyclic amines such as 4,4'-diaminodicyclohexylmethane, aromatic amines such as 4,4'-diaminodiphenyl, tetramines such as 2,4,6-tri(dimethylaminomethyl)phenol, etc. can be mentioned. In addition, these various compounds may be used individually by 1 type, and may be used in combination of 2 or more types. The total amount of the polyol compound and polyamine compound used as such reinforcing agents is not particularly limited, but the total amount is usually 1 to 500 parts by weight per 100 parts by weight of the hydroxyl group-containing liquid diene polymer. It is suitable to incorporate 3 to 300 parts by weight, preferably 3 to 300 parts by weight. Furthermore, fillers that can be optionally added to the liquid polymer composition depending on the intended use of the product include known inorganic fillers, such as mica, graphite, vermiculite, calcium carbonate, Examples include slate powder. The blending ratio of these inorganic fillers is not particularly limited, but based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer,
A suitable amount is 10 to 10,008 parts by weight, preferably 50 to 500 parts by weight. Furthermore, a plasticizer such as dioctyl phthalate may be added to the liquid polymer composition as a viscosity modifier, a softener such as aromatic, naphthenic, or paraffinic oil may be added, and adhesive strength and adhesive strength may be added. In order to adjust the temperature, tackifier resins such as alkylphenol resins, terpene resins, terpenephenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic and aromatic petroleum resins can be added in appropriate amounts depending on the application. can. In addition, appropriate amounts of curing accelerators such as dibutyltin dilaurate, stannous octoate, and polyethylene diamine, antiaging agents to improve weather resistance, and silicon compounds as antifoaming agents can be added according to conventional methods. Furthermore, the liquid polymer composition according to the present invention includes:
A composition is prepared by adding 10 to 800 parts by weight, preferably 30 to 500 parts by weight of sand, crushed stone, glass balloons, fly ash, perlite, etc. as aggregates to 100 parts by weight of the hydroxyl group-containing liquid diene polymer. The hardness can also be adjusted. Furthermore, a hydrocarbon solvent such as xylene, kerosene, mineral spirits, or rubber volatile oil may be added as a solvent to the liquid polymer composition. The liquid polymer composition according to the present invention can be obtained by blending and mixing the above-mentioned raw materials. The blending method is not particularly limited and may be carried out by any method, but usually, the above-mentioned blending raw materials, preferably excluding the polyisocyanate compound, solid rubber chips, and aggregate, are first blended, and the mixture is heated at a temperature of 15 to Stir at 120°C, preferably 70-100°C, for 5-240 minutes, preferably 30-180 minutes,
Next, a polyisocyanate compound is added to this mixture and stirred at a temperature of 0 to 70°C, preferably 15°C to 50°C, for 1 second to 240 minutes, preferably 5 seconds to 180 minutes, and then solid rubber chips and aggregate are mixed. A method of preparing a liquid polymer composition by stirring the mixture for 2 to 30 minutes, preferably 5 to 10 minutes at a temperature of 0 to 70°C, preferably 15 to 50°C, can be suitably employed. The above blending and mixing can be performed using a conventional kneading machine such as a paddle mixer, a Banbury mixer, a roll mill, or the like. The laminate of the present invention can be manufactured by applying the liquid polymer composition prepared as described above to a substrate to a predetermined thickness and curing the composition under predetermined conditions. As the substrate to be used, ordinary ones can be used, specifically, for example, wooden boards, wooden boards,
Examples include calcium silicate board, fly ash cement board, asbestos cement perlite board, pulp cement board, wood chip cement board, decorative pulp cement board, decorative asbestos cement board, and decorative pulp selent perlite board. Further, the laminate of the present invention can also be obtained by performing a laminate curing treatment using the liquid polymer composition as an intermediate layer having a predetermined thickness between two desired substrates. That is, the laminate of the present invention has any of the following structures: a structure in which the cured layer obtained by curing the liquid polymer composition is a surface layer, a structure in which it is an intermediate layer, and a structure in which it is a surface layer and an intermediate layer. It can be obtained as a laminate consisting of a predetermined number of layers. The conditions for the curing treatment cannot be uniformly defined because they vary depending on the composition of the liquid polymer composition used, but for example, usually at 0 to 120°C, preferably 15 to 70°C, for 0.5 to 80 hours, Preferably, it can be carried out within a range of 1 to 75 hours. If this curing temperature is too low, curing may be insufficient or adhesion between layers may be insufficient.
On the other hand, if the curing temperature is too high, desired physical properties may not be obtained. Note that this hardening treatment can be performed in combination with press working or compression molding treatment such as pressure roll working, and usually this press working etc. is performed under the conditions of the hardening treatment, which also serves as hardening treatment. It is desirable to carry out this process, and pre-curing treatment and post-curing treatment can also be carried out as appropriate before and after this compression molding process. In addition, the laminate of the present invention is produced by subjecting the liquid polymer composition to a curing treatment separately from the substrate to produce a layered cured product, and then applying the cured product to the desired shape as described above using an adhesive. It can also be obtained by stacking it on a substrate and performing an adhesive lamination process. Although ordinary adhesives can be used as this adhesive, the liquid polymer composition described above may also be used. The laminate of the present invention can be obtained in various thicknesses and sizes depending on its use. The thickness of each layer is not uniform depending on the application, so it cannot be specified uniformly, but usually, for example, the thickness of the cured material layer is
It is suitable that the thickness of the substrate is 1 to 20 mm, preferably 2 to 10 mm, and the thickness of the substrate is 0.2 to 10 mm, preferably 0.5 to 8 mm. By setting the thickness of the cured layer within the above range, the properties of the laminate of the present invention as a building material or structural material, particularly soundproofing and vibration-proofing properties, can be more effectively exhibited. In the manner described above, it is possible to produce the laminate of the invention in which the substrate and the cured layer of the liquid polymer composition are firmly laminated and adhered. The thus obtained laminate of the present invention has significantly improved soundproofing and vibration-proofing properties compared to conventional ones, and is also excellent in other basic properties as a building material or structural material. For example,
It can be suitably used as building materials such as flooring materials, wall materials, ceiling materials, and various other structural materials. [Effects of the Invention] According to the present invention, the soundproofing properties and vibrationproofing properties are significantly improved, and the present invention is significantly improved in practical use, and can be suitably used as building materials such as flooring materials, wall materials, ceiling materials, and other structural materials. An excellent laminate can be provided. [Example] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the soundproofing properties and vibrationproofing properties in each example were tested as follows. (1) Soundproofing: The laminate obtained in each example was held horizontally on a support, and a sound level meter (manufactured by Denshi Sokki Kogyo Co., Ltd.,
A microphone connected to a type 1015) was placed, and the noise generated by hitting the laminate was expressed in dB. (2) Vibration damping properties: ^A test piece (1× 5 x 50 mm) was repeatedly vibrated using an oscillator (manufactured by Toyo Baldwin Co., Ltd., model DDV-11-C, frequency 11 Hz), and its dissipation rate (tan δ) was measured. This dissipation rate is an angle that indicates the time lag between the stress and strain applied to the test piece, and has the following meaning. tanδ=C″/C′ where C″=storage modulus (equivalent to energy stored or released per cycle) C′=loss modulus (equivalent to energy dissipated or lost per cycle) ) Example 1 (i) Production of liquid polymer composition Among the components shown in Table 1, the components excluding the polyisocyanate compound and solid rubber chips were
The mixture was stirred at a temperature of 80°C for 3 hours, then the amount of polyisocyanate compound shown in Table 1 was added, and the mixture was stirred at a temperature of 20°C for 3 hours. Subsequently, solid rubber chips were added and stirred for 15 minutes at a temperature of 20°C to produce a liquid polymer composition. (ii) Manufacture of laminate The above liquid polymer composition was mixed into 300×300×0.5
Coated on decorative plywood of mm, 120℃, 200Kg/cm ² , 15
A laminate was obtained by pressing for a minute. The thickness of the cured composition layer of this laminate was 3 mm. Example 2 A liquid polymer composition having the composition shown in Table 1 was prepared, and a laminate was manufactured in the same manner as in Example 1 using a slatted board as a substrate. The vibration damping properties in this case are shown in Table 1. Example 3 A liquid polymer composition having the composition shown in Table 1 was prepared, and this composition was used as an intermediate layer between two calcium silicate plates of 300 x 300 x 6 mm under the same conditions as in Example 1. A laminate was obtained by pressing. The thickness of the composition cured layer of this laminate was 1 mm.
The soundproofing properties and vibrationproofing properties in this case are shown in Table 1.

[Table] *3 Comparative example of 1 mm cubic shape 1 100 parts by weight of brominated butyl rubber with 2 mol% isoprene content (bromine content 2.2% by weight), 400 parts by weight of liquid polybutene, 20 parts by weight of silica, 2 parts by weight of trimethylolpropane triacrylate , 2 parts by weight of benzoyl isopropyl ether, and 2,2'-methylenebis(4-methyl-6-t-butylphenol) is applied to decorative plywood, and this is cured by ultraviolet irradiation to form a laminated layer. manufactured the body. The soundproofing properties and vibrationproofing properties of this product are shown in Table 2. Comparative Example 2 A laminate was manufactured by repeating the same operations as in Comparative Example 1 using a laminate board instead of a decorative board. The soundproofing properties and vibrationproofing properties of this product are shown in Table 2. Comparative Example 3 The composition was sandwiched between two calcium silicate plates,
Comparative example 1 except that it was cured with a sandwich structure
The same operation was repeated to produce a laminate. The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1. On the substrate surface, a hydroxyl group-containing liquid diene polymer,
A laminate comprising a cured layer of a liquid polymer composition comprising a polyisocyanate compound and solid rubber chips.