JPH0660248B2 - Damping material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vibration damping material that reduces noise of power equipment and protects precision equipment from external vibration.

[Conventional technology]

In addition to the reduction of noise of power equipment, in recent years, demands for precision processing, precision measurement, etc. have increased, and various damping materials have been proposed. For example, (a) a method of attaching a rubber sheet, a soft plastic sheet or the like to the structural material with an adhesive,
(B) A method of applying a coating material containing a resin such as a liquid or solution epoxy resin, polyurethane resin, unsaturated polyester resin, etc., and a scale-like filler such as minor powder, glass flakes, etc. to the structural material, (c) A method of mixing a metal fiber with an unsaturated polyester resin, an epoxy resin or the like and molding the mixture has been proposed.

However, it is difficult to apply the method (a) to a molded product having a complicated surface shape, and the method (b) suppresses vibration due to uneven coating thickness, particularly uneven thickness due to paint sag on the vertical surface. Large variations in performance. Further, although the method (c) makes it easy to form a curved surface, it has the drawback of increasing the weight of the molded product, and its vibration damping property at low temperatures is insufficient.

As described above, the conventional technique has advantages and disadvantages, stably exhibits damping properties in any shape, is economical and excellent in productivity, and has good damping properties in a wide temperature range including a low temperature range. It is desired to develop a damping material that has

[Problems to be solved by the invention]

The present invention provides a vibration damping material having excellent vibration damping properties in a wide temperature range of, for example, −20 ° to + 100 ° C., and having excellent moldability capable of stably exhibiting damping properties in any shape. The purpose is to provide.

[Means for solving problems]

The present invention includes (A) a monomer (a) having two or more radically polymerizable unsaturated groups in one molecule, and a monomer having an alkylene group having 4 or more carbon atoms and / or an alkylene ether group in one molecule. An unsaturated resin obtained from a raw material containing at least a monomer (b), (B) a radically polymerizable monomer, and (C) a radical polymerization initiator are mixed with an organic fiber or In a vibration damping material obtained by impregnating a non-woven fabric or woven fabric of inorganic fibers and molding and thermosetting, The weight ratio of the unsaturated resin (A) and the radical polymerizable monomer (B) is 30 to 95% based on the total weight: 70 to 5
%, 2. The content of the alkylene group having 4 or more carbon atoms and / or the alkylene ether group in the monomer (b) is 20 to 7 based on the total weight of the (A) unsaturated resin and the (B) radically polymerizable monomer.
0% by weight, and 3. The glass transition point of the cured product of the liquid composition is −10 ° C. to +
It is a vibration damping material having a temperature of 30 ° C.

The (A) unsaturated resin comprises a monomer (a) having two or more radically polymerizable unsaturated groups in one molecule and an alkylene group or alkylene ether group having 4 or more carbon atoms in one molecule. A monomer (b) having, for example, a polyhydric alcohol having these groups, a polycarboxylic acid and / or an isocyanate compound having these groups as a raw material,
By subjecting these compounds to acryloyl modification, methacryloyl modification or allyl modification, they can be produced by a known method. For example, (a) maleic anhydride,
Fumaric acid, unsaturated dibasic acids having radically polymerizable unsaturated groups such as itaconic acid, and / or adipic acid, sebacic acid,
Aliphatic dibasic acids having an alkylene group having 4 or more carbon atoms, such as azelaic acid, dodecanedioic acid, hexadecanedioic acid, and eicosanedioic acid, and butanediol, bentanediol,
Method by esterification reaction with polyhydric alcohol having alkylene group or alkylene ether group having 4 or more carbon atoms, such as hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (glass transition of cured product In the range where the point does not exceed 30 ℃,
An aromatic dibasic acid such as phthalic acid, or a polyhydric alcohol having no alkylene group having 4 or more carbon atoms or an alkylene ether group such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and neopentyl glycol may be used in combination. . (B) Esterification reaction of acrylic acid or methacrylic acid with a polyhydric alcohol having an alkylene group having 4 or more carbon atoms or an alkylene ether group, or a hydroxy-terminated saturated or unsaturated polyester resin prepared from these , Or a method in which an acryloyl group or a methacryloyl group is introduced at the molecular end by a transesterification reaction with an acrylic acid ester or a methacrylic acid ester (C) Polyvalent having an alkylene group or alkylene ether group having 4 or more carbon atoms Carboxylic acid, or a carboxyl-terminated saturated or unsaturated polyester resin obtained by using these as a raw material, and a hydroxyalkyl ester of acrylic acid or methacrylic acid, or an esterification reaction with allyl alcohol to form an acryloyl group, a methacryloyl group or allyl at the molecular end. Introduced the group Method for obtaining (d) A hydroxy-terminated compound similar to (b), and a diisocyanate compound having an alkylene group having 4 or more carbon atoms or an alkylene ether group such as hydroxyalkyl ester of acrylic acid or methacrylic acid and hexamethylene diisodianate (E) An unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, or the above-mentioned unsaturated dibasic acid is added to a diepoxide compound having an alkylene group or an alkylene ether group having 4 or more carbon atoms. Can be obtained by addition reaction.

These methods can be used in combination, and the unsaturated resins obtained by different methods can be mixed and used.

In the above-mentioned (A) unsaturated resin, using the monomer (b) containing an alkylene group having 4 or more carbon atoms and an alkylene ether group as a raw material is essential for imparting damping properties in a wide temperature range. is there. The content of these groups is preferably 20% by weight or more based on the total amount of the (A) unsaturated resin and the (B) radically polymerizable monomer, and particularly 25 to
70% by weight is preferred.

The (B) radically polymerizable monomer used in the present invention is a diluent for sufficiently impregnating the above-mentioned (A) unsaturated resin into a non-woven fabric or a woven fabric, and reacts radically with the unsaturated resin. , A so-called reactive diluent that forms a cured product. For example, aromatic monomers such as styrene, vinyltoluene, and paramethylstyrene; and methacrylic acid esters such as methyl methacrylate and butyl methacrylate are preferably used.

The amount of the radical polymerizable monomer (B) used is (A)
It is usually 5% by weight or more, preferably 10 to 70% by weight, based on the total amount of the unsaturated resin and the radically polymerizable monomer (B). If this amount exceeds 70% by weight, not only it is difficult to set the glass transition point of the cured product of the liquid composition to 30 ° C. or lower, but also the workability during molding is deteriorated, which is not suitable. If this amount is less than 5% by weight, the viscosity during molding is remarkably increased, the workability thereof is deteriorated, and the curing is insufficient, which is unsuitable.

In order to prepare the liquid composition of the present invention, a polymerization inhibitor is added to the above (A) unsaturated resin, if necessary, and the above (B)
A radical-polymerizable monomer is added, and if necessary, heated and mixed to dissolve, cooled, and a radical-polymerization initiator is added.

Here, the polymerization inhibitor is for preventing undesired polymerization from occurring during the preparation of the liquid composition and further before the impregnation of the liquid composition into the non-woven fabric or the woven fabric. . Examples of the polymerization inhibitor include known methylparaquinone and the like, and the amount thereof is usually 0.005 to 100 parts by weight of the total amount of the unsaturated resin (A) and the radical polymerizable monomer (B). 0.1 parts by weight.

The above radical polymerization initiator can be appropriately selected depending on the temperature at the time of laminate molding, and examples thereof include methyl ethyl ketone peroxide, acetylacetone peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl perbenzoate, and tert-butyl peroxide. Octoate, dicumyl peroxide,
When 1,1 bis 3,5,5-trimethylcyclohexanone or the like is used, and when it is further cured at room temperature, metal soaps such as cobalt naphthenate and cobalt octenoate and dimethylaniline are used as reaction accelerators.

The amount of the radical polymerization initiator used is usually 0.3 to 3.0 parts by weight per 100 parts by weight of the mixture of the (A) unsaturated resin and the (B) radically polymerizable monomer.

In the cured product of the liquid composition thus prepared, T
MA method (Thermo mechanical Ana
The glass transition point by the lysis method) is required to be 30 ° C or lower, preferably -10 to + 25 ° C. If it exceeds 30 ° C., the vibration damping property of the obtained material in the low temperature region becomes insufficient, which is unsuitable.

The organic fiber or inorganic fiber non-woven fabric or woven fabric used in the present invention, for example, glass fiber, carbon fiber, alumina fiber, rock wool, polyester fiber, rayon fiber,
There are non-woven fabrics or woven fabrics such as nylon fibers and aromatic polyamide fibers, and these fibers may be metal-deposited or metal-plated. Further, when the shape to be laminated and formed is a complicated curved surface, a nonwoven fabric is more preferable.

The above liquid composition is impregnated into a non-woven fabric or a woven fabric, and laminated according to a desired thickness and molding is carried out.As a molding method, a hand layup method, a resin injection method, a metal matched die method or the like is used, In order to rapidly perform the curing by the radical polymerization reaction, the mold is preferably heated to 80 to 160 ° C. and pressurized to 10 to 200 kg / cm ² to perform molding and curing.

Further, the above-mentioned vibration-damping material of the present invention before curing is impregnated with a resin showing a high glass transition temperature by a non-woven fabric or woven fabric of the same form, that is, SMC (sheet molding compound) or the like, or metal or the like. It is also possible to laminate the sheets of different materials at the same time and mold and thermoset them for use. In the case of a composite laminate of different material sheets, in order to obtain a sufficient vibration damping effect, the thickness of the vibration damping material layer of the present invention is 10% or more, more preferably 15% or more of the thickness of the entire laminate after curing. is there.

Also, in practical use, a colorant in the liquid composition used above,
Auxiliaries such as fillers, mold release agents, waxes, dispersion aids, and shrinkage reducing agents may be mixed and used together within a range that does not impair the effects of the present invention.

This will be described in more detail below with reference to examples.

〔Example〕

Example 1 70 parts by weight of an unsaturated polyester obtained by reacting 1.0 mol of maleic anhydride, 1.0 mol of adipic acid and 2.2 mol of 1,6-hexanediol with methylparaquinone as a polymerization inhibitor. 0.02 parts by weight, 30 parts by weight of styrene, and 1.0 part by weight of tert-butyl perbenzoate as a radical polymerization initiator were added, mixed and dissolved to obtain a liquid composition 1.

Table 1 shows the use ratios of the main raw materials (A) and (B) of the liquid composition. The content (% by weight) of the alkylene group having 4 or more carbon atoms in the raw material of the (A) unsaturated resin based on the total weight of the (A) unsaturated resin and the (B) radical-polymerizable monomer is It was calculated from the amounts of saturated polyester, styrene, maleic anhydride, adipic acid, and 1,6-hexanediol used. Further, the liquid composition was cured at 140 ° C., and the glass transition point of the cured product was measured by the TMA method and is shown in Table 1.

Next, the liquid composition 1 was impregnated into a polyester nonwoven fabric having a thickness of 1 mm. The impregnation ratio was liquid composition / polyester non-woven fabric = 85/15 (weight ratio).

Next, four non-woven fabrics impregnated with the liquid composition are superposed and molded under the conditions of a pressure of 100 kg / cm ² , a temperature of 140 ° C. and a molding time of 5 minutes, and a laminated molded plate of the present invention having a thickness of 3 mm is formed. Obtained the shaking material. The resin composition / nonwoven fabric weight ratio after molding was 78/22. Width of this molded plate is 10 mm,
The sample was cut into a length of 250 mm to obtain a sample for measuring vibration damping characteristics.

The vibration damping characteristics were measured with a B & K complex viscoelasticity measuring device manufactured by Brielkeer in Germany. The values of the loss coefficient (ηcomb) obtained by changing the temperature at a frequency of 500 Hz are shown in Table 2 and FIG.

Example 2 Unsaturated polyester obtained by reacting 1.0 mol of maleic anhydride, 1.0 mol of adipic acid, and 2.2 mol of diethylene glycol was further reacted with 0.2 mol of hexamethylene diisocyanate to give a urethanization derivative. 65 parts of saturated polyester, 0.02 of methylparaquinone, a polymerization inhibitor
By weight, 35 parts by weight of styrene and 1.0 part by weight of tert-butyl perbenzoate as a radical polymerization initiator were added and mixed to obtain Liquid Composition 2 of the present invention.

Table 1 shows the use ratios of the main raw materials (A) and (B) of the liquid composition. The content (% by weight) of the alkylene group having 4 or more carbon atoms and the alkylene ether group in the raw material of the (A) unsaturated resin based on the total weight of the (A) unsaturated resin and the (B) radical-polymerizable monomer is , And was calculated in the same manner as in Example 1. Further, the liquid composition was cured at 140 ° C., and the glass transition point of the cured product was measured by the TMA method and is shown in Table 1.

Next, the liquid composition 2 was impregnated into a polyester nonwoven fabric having a thickness of 1 mm. The impregnation ratio was liquid composition / polyester non-woven fabric = 85/15 (weight ratio).

Next, four non-woven fabrics impregnated with the liquid composition are superposed and molded under the conditions of a pressure of 100 kg / cm ² , a temperature of 140 ° C. and a molding time of 5 minutes to obtain a vibration damping material of the present invention in the form of a laminated molding plate having a thickness of 3 mm. Got the material. The weight ratio of the resin composition / nonwoven fabric after molding was 80/20. This molded plate was cut into a piece having a width of 10 mm and a length of 250 mm, and used as a sample for measuring vibration damping characteristics. The loss coefficient was measured in the same manner as in Example 1 and shown in Table 2 and FIG.

Example 3 Trifunctional polypropylene glycol (molecular weight 700) 1.
0 mol, hydroxyethyl methacrylate 3.0 mol,
60 parts by weight of an unsaturated polyurethane obtained by reacting 3.0 mol of hexamethylene diisocyanate, 0.02 part by weight of a polymerization inhibitor methyl paraquinone, 20 parts by weight of styrene,
20 parts by weight of butyl methacrylate and 1.0 part by weight of tert-butyl perbenzoate as a radical polymerization initiator were added, mixed and dissolved to obtain a liquid composition 3 of the invention.

Table 1 shows the use ratios of the main raw materials (A) and (B) of the liquid composition. The content (% by weight) of the alkylene group having 4 or more carbon atoms in the raw material of the (A) unsaturated resin based on the total weight of the (A) unsaturated resin and the (B) radically polymerizable monomer is the same as in Example 1.
It was calculated in the same manner as. Further, the liquid composition
Cured at 40 ℃, the glass transition point of the cured product is TMA
It is measured by the method and shown in Table 1.

Next, the liquid composition 3 was impregnated into a polyester nonwoven fabric having a thickness of 1 mm. The impregnation ratio was liquid composition / polyester non-woven fabric = 85/15 (weight ratio).

Next, four non-woven fabrics impregnated with the liquid composition are superposed on each other, and the pressure is 1
Molding was performed under the conditions of 00 kg / cm ² , temperature of 140 ° C. and molding time of 5 minutes to obtain a laminated molded plate-shaped damping material of the present invention having a thickness of 3 mm. The resin composition / nonwoven fabric weight ratio after molding was 79/21. This molded plate was cut into a piece having a width of 10 mm and a length of 250 mm, and used as a sample for measuring vibration damping characteristics. The loss coefficient was measured in the same manner as in Example 1 and shown in Table 2 and FIG.

Comparative Example 1 Maleic anhydride 1.2 mol, phthalic anhydride 0.8 mol,
60 parts by weight of an unsaturated polyester obtained by reacting 1.50 mol of propylene glycol and 0.64 mol of diethylene glycol, 0.02 part by weight of a polymerization inhibitor methyl paraquinone, 40 parts by weight of styrene and tertiary as a radical polymerization initiator. 1.0 part by weight of butyl perbenzoate was added and mixed and dissolved to obtain a liquid composition 4.

Table 1 shows the use ratios of the main raw materials (A) and (B) of the liquid composition. The content (% by weight) of the alkylene ether group having 4 or more carbon atoms in the raw material of the (A) unsaturated resin based on the total weight of the (A) unsaturated resin and the (B) radical-polymerizable monomer is
Calculation was performed in the same manner as in Example 1. Further, the liquid composition was cured at 140 ° C., and the glass transition point of the cured product was measured by the TMA method and is shown in Table 1.

Next, the liquid composition 4 was impregnated into a polyester nonwoven fabric having a thickness of 1 mm. The impregnation ratio was liquid composition / polyester non-woven fabric = 85/15 (weight ratio).

Next, four non-woven fabrics impregnated with the liquid composition are superposed and molded under the conditions of a pressure of 100 kg / cm ² , a temperature of 140 ° C. and a molding time of 5 minutes to obtain a vibration damping material of the present invention in the form of a laminated molding plate having a thickness of 3 mm. Got the material. The weight ratio of the resin composition / nonwoven fabric after molding was 80/20. This molded plate was cut into a piece having a width of 10 mm and a length of 250 mm, and used as a sample for measuring vibration damping characteristics. The loss coefficient was measured in the same manner as in Example 1 and shown in Table 2 and FIG.

Comparative Example 2 Maleic anhydride 1.6 mol, isophthalic acid 0.4 mol,
55 parts by weight of an unsaturated polyester obtained by reacting 1.04 mol of propylene glycol and 1.04 mol of neopentyl glycol, with 0.05 part of a polymerization inhibitor methylparaquinone
2 parts by weight, 45 parts by weight of styrene and 1.0 part by weight of tert-butyl perbenzoate as a radical polymerization initiator were added, mixed and dissolved to obtain a liquid composition 5.

None of the raw materials used for the composition have an alkylene group having 4 or more carbon atoms or an alkylene ether group. The liquid composition was cured at 140 ° C., and the glass transition point of the cured product was measured by the TMA method.

Next, the liquid composition 5 was impregnated into a polyester nonwoven fabric having a thickness of 1 mm. The impregnation ratio was liquid composition / polyester non-woven fabric = 85/15 (weight ratio).

Next, four non-woven fabrics impregnated with the liquid composition are superposed on each other, and the pressure is 1
Molding was performed under the conditions of 00 kg / cm ² , temperature of 140 ° C. and molding time of 5 minutes to obtain a laminated molded plate having a thickness of 3 mm. The resin composition / nonwoven fabric weight ratio after molding was 78/22. This molded plate was cut into a piece having a width of 10 mm and a length of 250 mm, and used as a sample for measuring vibration damping characteristics. The loss coefficient was measured in the same manner as in Example 1 and shown in Table 2 and FIG.

Examples 4 to 6 Estermat XGH1001 (trade name, manufactured by Mitsui Toatsu Kagaku Co., Ltd.), which is a general-purpose nonwoven polyester SMC, is used for the liquid composition-impregnated nonwoven sheets obtained in Examples 1 to 3, respectively.
Sandwiching (thickness 2 mm) and hot pressing under conditions of 140 ° C., 100 kg / cm ² and 5 minutes according to ordinary SMC molding to obtain a laminated molded plate-shaped damping material of the present invention having a thickness of 3 mm. . The thickness of the liquid composition-impregnated nonwoven fabric sheet cured product layer of the present invention in the laminated cured product was about 20% of the whole. The damping characteristics of these were measured in the same manner as in Example 1, and the measurement results are shown in Table 3 and FIG.

Comparative Example 3 A molding plate having a thickness of 3 mm was prepared under the same conditions as in Example 3 by combining only three Estermat XGH1001 used in Examples 4 to 6, and the vibration damping characteristics were measured in the same manner as in Example 1. The results are shown in Table 3 and FIG.

As described above, the damping material of the present invention shown in the examples is -20 ° C. to + 100 ° C., whether it is used alone as in Examples 1 to 3 or combined with other materials as in Examples 4 to 6. It was confirmed that the damping effect was sufficiently exhibited in the temperature range.

〔The invention's effect〕

As described in detail above, according to the present invention, −20 ° C. to +
It is possible to easily obtain a vibration damping material having an excellent vibration damping property in a wide temperature range of 100 ° C. and having an arbitrary curved surface.

[Brief description of drawings]

FIG. 1 is a diagram showing the damping characteristics of the three types of single-layer laminated plate-shaped vibration damping materials of the present invention and two types of comparative molded products as a relationship between loss coefficient and temperature, and FIG. 2 is a general-purpose SMC. FIG. 3 is a diagram showing the damping characteristics of three laminated molded plate damping materials of the present invention and one comparative molded article sandwiched with each other as a relationship between loss coefficient and temperature.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-49-44095 (JP, A) JP-A-56-153137 (JP, A) Practical application Sho-59-117644 (JP, U)

Claims (3)

[Claims] 1. A monomer (a) having (A) two or more radically polymerizable unsaturated groups in one molecule, and an alkylene group having 4 or more carbon atoms and / or an alkylene ether group in one molecule. An unsaturated resin obtained from a raw material containing at least the monomer (b), (B) a radical-polymerizable monomer, and (C) a radical polymerization initiator are mixed into a liquid composition, Alternatively, in a vibration damping material obtained by impregnating a nonwoven fabric or a woven fabric of inorganic fibers and molding and thermosetting, The weight ratio of the unsaturated resin (A) and the radical polymerizable monomer (B) is 30 to 95% based on the total weight: 70 to 5
%, 2. The content of the alkylene group having 4 or more carbon atoms and / or the alkylene ether group in the monomer (b) is 20 based on the total weight of the unsaturated resin (A) and the radical polymerizable monomer (B). ~ 70% by weight, and 3. The glass transition point of the cured product of the liquid composition is -1.
A damping material having a temperature of 0 ° C to + 30 ° C.