JPS61270154A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a laminate, and more particularly, to a laminate that has excellent vibration-damping, heat-insulating, and sound-absorbing properties and is useful as a variety of structural materials.

[Prior Art] Traditionally, wood boards,
A laminate is known in which a resin plate, a metal plate, or the like is laminated with a layer made of a cured product of a composition made of a hydroxyl group-containing liquid diene polymer and a polyisocyanate compound.

[Problem to be Solved by the Invention 1 This laminate is a material that is lightweight, has high rigidity, and excellent water resistance.However, especially when used as a building material, it has poor vibration damping properties, The heat insulation and sound absorption properties are not necessarily satisfactory, and there is still room for improvement.

[Means for Solving the Problems] The present invention aims to solve the conventional problems and provide a laminate having excellent vibration damping properties, heat insulation properties, and sound absorption properties.

As a result of extensive research in order to achieve the above object, the present inventors discovered that, in place of the conventional cured layer of a composition consisting of a hydroxyl group-containing liquid diene polymer and a polyisocyanate, the 2J&min. The present invention was completed after confirming that good properties can be obtained by using a cured layer of a novel composition containing a filler as a constituent layer of a laminate.

That is, the laminate of the present invention is characterized by having at least one layer made of a cured product of a composition containing a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a wood filler.

[Specific Description] As described above, the carcass a of the present invention includes at least one layer of a cured product of a composition containing a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a wood filler as a constituent layer. It is a thing.

The constituent material of the layer combined with such a cured body layer is not particularly limited, and examples thereof include a wooden board, a resin board, a metal board, a ceramic board, paper, and cloth. Among these, wood boards, resin boards, metal plates, etc. are suitable as structural materials. Furthermore, the number of constituent layers of the laminate of the present invention is not limited at all. For example, in the case of a three-layer laminate, if the cured product layer of the above composition is an intermediate layer, the cured This is advantageous because the body layer has the function of adhering the upper and lower layers together.

Further, in the laminate of the present invention, the layer thickness of each constituent layer may be appropriately set depending on the material of the constituent layer or the use of the laminate, but usually the thickness of the cured layer is 1 to 10s layer, etc. It is preferable to set the layer thickness of each of the constituent layers to about 0.5 to 5 layers.

In the laminate of the present invention, the composition forming the cured body layer will be explained below. This composition is.

As mentioned above, this is a liquid polymer composition containing a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a wood filler as essential components.

First, the hydroxyl group-containing liquid diene polymer, which is the first essential component, is a liquid diene polymer having hydroxyl groups (OH groups) within 5 molecules, preferably at the end of the molecule, and has a number average molecular weight of 300 to 25,000. Especially 500-10000
Preferably.

These liquid diene polymers include diene polymers and diene copolymers having 4 to 12 carbon atoms, and copolymers of these diene monomers and α-olefinic addition polymerizable monomers having 2 to 22 carbon atoms. There is. Specifically, butane diene homopolymer, imprene homopolymer, butadiene-styrene copolymer, phtadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer,
Examples include butadiene-n-octadecyl acrylate copolymer. These liquid diene polymers are produced by, for example, adding a conjugated diene monomer to a liquid reaction medium in the presence of hydrogen peroxide.

It can be produced by heating reaction.

Furthermore, the OH group content of this hydroxyl group-containing liquid diene polymer is 0. INIOmeq/H further, 0.3 to 5,
Preferably it is Omeq/g.

Next, the polyisocyanate compound, which is the second essential component, is an organic compound having two or more incyanate groups in one molecule, and is an organic compound that has two or more incyanate groups in one molecule, and has a high activity of the active hydrogen group-containing liquid diene polymer and the polyol compound. Reactive isocyanate groups toward hydrogen-containing functional groups (NCO
It has the group )゛. Examples of polyisocyanate compounds include the usual aromatic, aliphatic and cycloaliphatic ones, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI), liquid modified diphenylmethane diisocyanate, polymethylene Polyphenylinocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, cyclohexanephenylene diisocyanate, naphthalene-1,5-diisocyanate, isopropylbenzene-2,4-diisocyanate, polypropylene glycol and tolylene diisocyanate addition reaction product, etc., among others [01, Liquid modified diphenylmethane diisocyanate, tolylene diisocyanate and the like are preferred.

The amount of the polyisocyanate compound to be blended is not particularly limited, but the ratio of the polyisocyanate groups of the polyisocyanate compound to the hydroxyl groups of the hydroxyl group-containing liquid diene polymer (NCO group 10H group) is 0.2~! 0
．． It is preferable to set it to 0, more preferably 0.5 to 6.0.

Furthermore, the type, shape, size, etc. of the wood filler, which is the third essential component of this composition, are not particularly limited; for example, wood flour may be used.

Suitable materials include wood chips and wool.

The amount of this wood filler is not particularly limited, but it is preferably set at 5 to 300 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer. .

Furthermore, in the liquid polymer composition of the present invention, in addition to the above-mentioned three essential components, the following additives may be added as appropriate.

That is, first, examples of reinforcing agents include polyol compounds and polyamine compounds.

The polyol compound is not particularly limited, and any of primary polyol, secondary polyol, and tertiary polyol may be used. Specifically, for example, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol. , 1.3-butanediol, 2,3-butanediol, 1.2-bentanediol, 2.3-bentanediol, 2.5-hexanediol, 2.4-hexanediol, 2-ethyl-1,3 - at least one dihydrogen such as hexanediol, cyclohexanediol, glycerin, N,N-bis-2-hydroxypropylaniline, N,N'-bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A, etc. Examples include low molecular weight polyols containing hydroxyl groups bonded to carbon atoms.

Furthermore, in the present invention, ethylene glycol which does not contain a hydroxyl group bonded to a secondary carbon as a polyol, 1.
3-propylene glycol, 1,4-butanediol,
1,5-bentanediol, 1,8-hexanediol, etc. can also be used. Diols are usually used as the polyols used in the present invention, but triols and tetraols may also be used, and their molecular weights are 50 to 500.
It is within the range of .

Further, the polyamine compound is not particularly limited and may be any of diamine, triamine, and tetramine, and furthermore, any of primary polyamine, secondary polyamine, and tertiary polyamine may be used. Examples of polyamine compounds include aliphatic amines such as hexamethylene diamine; aliphatic amines such as 3,3'-dimethyl I and 4'-diaminodicyclohexylmethane; aromatic amines such as 4,4-diaminodiphenyl; 2,4.8-1li (
Examples include tetramines such as (dimethylaminomethyl)phenol.

The amount of the reinforcing material as described above, that is, the polyol compound and the polyamine compound, is based on 100 parts by weight of the above-mentioned hydroxyl group-containing liquid diene polymer.

It is preferably set at 1 to 1000 parts by weight, particularly 3 to 200 parts by weight.

Next, 5411 fillers include mica, graphite, vermiculite, calcium carbonate, slate powder, etc. In addition, plasticizers such as dioctyl phthalate are added as viscosity modifiers, aromatic, naphthenic, paraffinic oils, etc. To further adjust the adhesion and adhesion strength, add a softener or use alkylphenol resins, terpene resins, terpenephenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, chroman resins, aliphatic and aromatic petroleum resins. It is also possible to add tackifying resins such as. Further, curing accelerators such as dibutyltin dilaurate, stannous octoate, polyethylene diamine, etc. can also be added. Furthermore, an anti-aging agent can be added to improve weather resistance, and a silicon compound or the like can be added as an antifoaming agent.

In addition to the above additives, it is also possible to add bituminous substances. Examples of bituminous materials include petroleum asphalts such as straight asphalt, blown asphalt, semi-prone asphalt, and base asphalt using propane as a solvent; petroleum pitch; petroleum tar; and coal pitch. The blending amount of these bituminous substances is 10 to 10 parts by weight per 100 parts by weight of the hydroxyl group-containing liquid diene polymer.
It is preferable to set the amount to about 0◎ parts by weight.

The liquid polymer composition used in the present invention can be easily prepared as follows. That is, first, predetermined amounts of the hydroxyl group-containing liquid diene polymer and other additives are respectively blended and mixed by stirring, at a temperature of 10-120°C, preferably 20-100°C, Wl
The stirring time is set to 1 to 380 minutes, preferably 5 to 180 minutes.

Next, predetermined amounts of a polyisocyanate compound and a wood filler are added to the resulting mixture, and the mixture is stirred and mixed again to obtain the desired composition. The temperature at this time is 10 to 100°C, preferably 20 to 80°C,
Stirring time is 1 second to 360 minutes.

Preferably, they are each set to t-tso minutes.

Furthermore, the laminate of the present invention can be manufactured as follows. First, the above-mentioned liquid polymer composition is applied to a layer other than the cured material layer among the constituent layers constituting the laminate, for example, a wooden board, and then cured under predetermined conditions. At the same time as forming a cured body layer, the cured body layer is adhered onto a wooden board to complete a laminate. The curing conditions at this time are a temperature of θ to 200°C, preferably 50°C.
~150°C, time 0.5~24 hours, preferably 1
It is preferable to set the time in increments of about 15 hours.

Also, for example, using a press molding machine etc., the molding pressure is 5 to 5.
It can also be hardened and molded at 300 kg/cm.

[Example] Reference Example (Preparation of Liquid Polymer Composition) Using each component described below, each liquid polymer composition used in Examples 1 to 3 described later was prepared.

(1) Hydroxyl group-containing liquid diene polymer Bi-terminal hydroxyl group liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd., R-45HT; number average molecular weight 280G, OR content 0.79meq/g
) (2) Polyisocyanate compound Nidiphenylmethane diisocyanate (3) Wood filler: A. Wood flour (sawdust, 10 mesh) B. Wood flakes (sawdust, 0.7X IOX 20) (4) Polyol compound : C0 propylene oxide adduct of bisphenol A, N,N-bis(2-hydroxypropyl)aniline (5) Plasticizer nidioctyl phthalate (6) Antiaging agent: E, 2.2°-methylenebis(4- Methyl-et
-butyl)phenol F, hentaerythrityl-tetrakis-3,5-di-t-butyl-4-hydroxyphenolpropionate 0, 2-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (7) Curing accelerator Nidibutyltin laurate Each of the above components is used in the amounts shown in Table 1, and all other components except the polyisocyanate compound and wood filler are placed in a glass container. mixed inside. Then into this mixture.

A wood filler previously dried at 105° C. for 1 hour was added and stirred for 1 minute at room temperature using a stainless steel rod. The wood filler was uniformly dispersed in the mixture only by this stirring. Then, by adding a polyisocyanate compound,
The liquid polymer composition of the present invention was obtained by stirring for 1 minute at room temperature using the same stainless steel rod.

Example 1 As shown in FIG. 1, the indicated composition was coated on a plywood board 1 with a thickness of 2 mm, and a press molding machine was used to mold the composition at 150° C. with a molding pressure of 200 kg/cnl. It was cured for 5 hours to form a cured body layer 2 having a thickness of three layers, thereby completing a laminate. This laminate was subjected to evaluation tests for vibration damping, heat insulation, and sound absorption, and the results are shown in the table. Note that these evaluation tests were conducted under the conditions shown below.

Vibration damping property: Loss coefficient by resonance method Insulation property: Heat mass flow resistance (based on JIS A1420)
rr1'-h -'0 /kcal) Sound absorption: JIS
300-10 by reverberation room method in accordance with A1409
Sound Absorption Coefficient at 00 Hz Example 2 A laminate as shown in FIG. 2 was produced by using the composition indicated as a cured layer and combining the cured layer with a layer made of polypropylene. That is, in Figure 1, the polypropylene layer 3.3° was used as the upper and lower layers, and the composition layer 4 was used as the intermediate layer, and the composition layer 4 was cured under the same conditions as in Example 1 to complete a laminate. The polypropylene layers 3.3 and 3.3 were both 2-layer thick, and the cured material layer was 3 mm thick.

Regarding the thus obtained laminate, various evaluation tests were conducted under the same conditions as in the above examples, and the results are shown in the table.

Example 3 A three-layer laminate was produced by using the indicated composition as the cured layer and combining the cured layer with an aluminum plate to have the cured layer as an intermediate layer as shown in FIG. did.

The thickness of the cured material layer was 3 mm, the thickness of the aluminum plate was 1 mm, and the curing conditions were the same as in Example 1 above. Regarding the laminate thus obtained,
Each evaluation test was conducted under the same conditions as in the above implementation and examples, and the results are shown in the table.

Comparative Example As shown, a conventional composition containing no wood filler was used as the cured layer, and the cured layer and plywood were combined to produce a two-layer laminate similar to that shown in FIG.

The curing conditions were set in the same manner as in Example 1, and the thickness of the cured material layer was 3 mm, and the thickness of the plywood was 2 mm. Regarding the thus obtained laminate, various evaluation tests were conducted under the same conditions as in the above examples, and the results are shown in the table.

[Effects of the Invention] As is clear from the above description, since the laminate of the present invention has a cured layer made of a novel composition as a constituent layer, it is different from a laminate using a cured layer made of a conventional composition. It has excellent vibration damping properties, heat insulation properties, and sound absorption properties compared to other materials, and is extremely useful as a structural material for buildings, vehicles, ships, and other objects, and its industrial value is great.

[Brief explanation of drawings]

Both FIG. 1 and FIG. 2 are cross-sectional views showing embodiments of the laminate of the present invention. l・・・・・・Plywood, 2.4・・・・・・・・・
Hardened body layer, 3.39... Aluminum plate.

Claims (1)

[Scope of Claims] 1. A laminate having at least one layer made of a cured product of a composition containing a hydroxyl group-containing liquid diene polymer, a polyisocyanate compound, and a wood filler. 2. The laminate according to claim 1, wherein the layer other than the layer made of the cured product is a wooden board, a resin board, or a metal board.