JPH03297634A - Production of vibration-damping material - Google Patents

Abstract

PURPOSE:To obtain a sheetlike vibration-damping material which is inhibited in deformation and melt sticking and excellent in stability by applying, impregnating or laminating the long-sized base material with resin composition for the thermosetting type vibration-damping material, heating and pressure-molding the base material stuck with the resin composition and advancing the curing reaction of the resin composition and applying or laminating the molded form with a pressure sensitive adhesive or an adhesive. CONSTITUTION:As the composition for thermosetting type vibration-damping material, resin composition is utilized wherein a filler, a hardening promotor, a radical polymerization initiator and a mold release agent, etc., are added to phenolic resin, epoxy resin and resin component consisting of the radical polymerization reactive components. The long-sized base material is applied, impregnated or laminated with this resin composition. This base material stuck with the resin composition is continuously heated and pressure-molded and the curing reaction of the resin composition is advanced. When this resin composition is utilized, curing reaction and radical polymerization reaction of phenolic resin and epoxy resin are simultaneously advanced. The molded form has an IPN structure and workability is good. Melt sticking and deformation of the sheetlike material are inhibited during preservation and transport. Then the obtained long-sized molded form is applied or laminated with the pressure sensitive adhesive or the adhesive.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing a sheet-shaped vibration damping material.

[Conventional technology]

Conventional polymer vibration damping materials are manufactured by adding fillers, etc. to resins and elastomers, and this material is applied or welded on site as is, or this material is stretched into a sheet. In many cases, they were cut on-site and pasted with adhesive or adhesive. In addition, when producing sound-absorbing and sound-insulating materials, there is a method in which a case is molded from special fibers and the surface is covered with a plastic film (Japanese Patent Laid-Open No. 51-95212), and a method in which a binder is applied to nonwoven fibers with different elastic moduli. A method of impregnating the fibers and laminating them (Japanese Patent Laid-Open No. 51-100178), a method of laminating a resin containing reinforcing fibers and a foaming agent on a reinforcing fiber layer impregnated with resin (Japanese Patent Laid-Open No. 53-102392) (publication), a method of applying an organic polymer to glass fabric to give it a specific porosity (
JP-A-54-141601), a method of fusing plastic films, etc. to textiles, fiberboards (JP-A-57-1999)
47647, Japanese Patent Application Laid-open No. 62-121033)
Another method has been reported in which a porous resin is applied to the fiber surface and a woven fabric is formed using this fiber (Japanese Patent Application Laid-Open No. 61-28434).

[Problem to be solved by the invention]

Since vibrations vary depending on the source, material, shape, etc. of the vibrating part, it is difficult to unambiguously determine the location, weight, etc. to which the damping material is attached. Therefore, ease of construction on site is an important factor in evaluating damping materials.

Conventional vibration materials are often installed by applying or welding a material composition directly to the vibrating site, or by cutting a stretched sheet and pasting it to the vibrating site using adhesive or adhesive. A method has been adopted. However, although the former method allows for attachment to the optimal location, it is difficult to expect good workability, and there is also the risk of contaminating the surrounding area with odors, solvents, etc. In addition, with the latter method, there are concerns about fusion and deformation between sheet-like materials during stacking and transportation, and with resin-like materials, there is a risk of collapse due to impact, etc., and there are also problems with storage stability. are doing.

The present invention solves these drawbacks by providing a highly stable sheet-like material that has excellent vibration damping effects, good workability, and suppresses deformation and fusion of materials during storage and transportation. The purpose is to continuously manufacture thermosetting vibration damping materials.

[Means to solve the problem]

That is, the present invention involves coating or impregnating a thermosetting vibration damping material resin composition on a continuously conveyed long base material, if the resin composition has a low viscosity; In the case of high viscosity, it is coated or laminated in the form of a sheet, and after laminating the obtained resin composition-coated base material alone or in multiple layers,
The curing reaction of the resin composition is progressed by continuous heating and pressure molding, and then a pressure-sensitive adhesive or adhesive is continuously applied to one or both sides of the obtained long molded product, or a sheet is formed. The present invention provides a method for manufacturing a vibration damping material characterized by lamination.

In the field of soundproofing and sound-absorbing materials for the purpose of noise reduction, there are methods of combining base materials and resin, and then foaming the resin layer to create bubbles to increase the sound-absorbing effect, and composites of base materials with different elastic moduli. There are known methods for increasing the soundproofing effect. However, all of these materials are aimed at suppressing the transmission of sound, and are essentially different from vibration damping materials that focus on workability and storage stability as in the present invention.

The thermosetting vibration damping material composition used for producing the vibration damping material of the present invention may be any composition as long as it can be cured to obtain a molded product having an IPN structure, but it can be uniformly mixed in an uncured state. A resin composition prepared by adding a filler, a curing accelerator, a radical polymerization initiator, a mold release agent, etc. to a resin component consisting of a phenol resin, an epoxy resin, a radical polymerization reaction component, etc. is preferably used. This resin composition is applied to a base material such as a woven or non-woven fabric made of organic fibers or inorganic fibers, or a fiber entangled body made of organic fibers or inorganic fibers processed into a net shape, and the resin composition is continuously conveyed. If the resin composition has a high viscosity, it can be coated or impregnated, or if the resin composition has a high viscosity, it can be coated or laminated in the form of a sheet, and the resulting resin composition-coated base material can be laminated singly or in multiple layers, and then continuously. The resin composition is molded under heat and pressure to advance the curing reaction. When the above resin composition is used, the curing reaction and radical polymerization reaction of the phenol resin and the epoxy resin proceed simultaneously, and the resulting molded product has an IPN structure, and has good workability and is easy to use during storage and transportation. It has the characteristics that the melting and deformation of the sheet-like material inside is suppressed, and the applicable temperature range can be freely set by selecting the resin composition.

The present invention will be explained in more detail.

The resin composition for a thermosetting vibration damping material used in the present invention has as essential components a phenol resin, an epoxy resin, a radical polymerization reaction component having radical polymerization ability, a filler, a curing accelerator, and a radical polymerization initiator. A mixture of flame retardants, plasticizers, mold release agents, pigments, etc. is preferably used.

Radical polymerization reaction components include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, 2-
Hydroxyethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, vinyl acetate, styrene , methyl vinyl ketone, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, and other monofunctional radical polymerization reaction components such as vinyl compounds having various substituents, and ethylene glycol diacrylate, Ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polyurethane acrylate, polyurethane methacrylate, 1.6-hexanediol diacrylate, 1.6-
hexanediol diacrylate, divinylbenzene,
A combination of polyfunctional radical polymerization reaction components such as diallyl phthalate, trimethylolpropane triacrylate, unsaturated polyester, and other polyfunctional vinyl compounds having various substituents is used. Furthermore, among these -functional radical polymerization reaction components and polyfunctional radical polymerization reaction components, two or more of each may be used in combination, but at least one or more of these polyfunctional radical polymerization reaction components It is preferable to include. It is preferable that the polyfunctional radical polymerization reaction component is contained in an amount of 10 to 30% by weight based on the total radical polymerization components.

On the other hand, phenolic resins include novolak-type phenolic resins, drying oils modified by reacting drying oils such as tung oil and linseed oil with phenols, and then reacting with aldehydes, or directly reacting with novolac-type phenolic resins. Novolac type phenolic resin, or novolac type phenolic resin modified with aromatic hydrocarbon resin such as xylene resin as necessary, resol type phenolic resin, drying oil modified resol type phenolic resin, aromatic hydrocarbon resin modified resol type phenolic resin etc.

The novolac type phenolic resin used in the present invention contains at least one selected from phenol, alkylphenols such as cresol, butylphenol, and nonylphenol, and aldehydes such as formaldehyde, formalin, and acetaldehyde, and paraformaldehyde and hexamethylenetetramine. One type of aldehyde selected from among aldehyde sources is treated with 4 ml of organic acid in the presence of an inorganic or organic acid catalyst such as hydrochloric acid, oxalic acid, or para-toluenesulfonic acid.
After reacting at 0-100°C for 1-4 hours, 170-1
It can be obtained by concentrating at 90°C. Furthermore, steam distillation may be performed in which free phenols and aldehydes are removed from the system by introducing a large amount of steam into the resin and distilling it off under reduced pressure.

Moreover, the molar ratio of phenols and aldehydes is 1:0.
4 to 1:0.85 is preferred; if it is less than 0.4, there will be too much unreacted phenol and moldability will be impaired. 0.85
If it exceeds this amount, there is a risk of gelation during the synthesis reaction, making it difficult to manufacture.

On the other hand, resol-type phenolic resins contain at least one selected from phenol and alkylphenols, at least one selected from aldehydes and aldehyde sources, and a basic compound such as potassium hydroxide, sodium hydroxide, ammonia, trimethylamine, etc. In the presence of a catalyst, 60~
After reacting at 100"C for 30-180 minutes,
It can be obtained by concentrating at 100°C.

Furthermore, steam distillation may be performed as in the case of novolac type phenolic resin.

In addition, the molar ratio of phenols and aldehydes is 1:1.
．． 1 to 1:3, and t:i and t to 1j1.4 are preferred. If it is less than 1.1, unreacted phenols remain;
．． If it exceeds 4, too much gas is generated at the time of curing, which impairs moldability.

There are two methods for modifying with drying oil, aromatic hydrocarbon resin, etc.: one is to synthesize a precursor before phenol resin synthesis, and the other is to modify it after phenol resin synthesis. However, the former method leaves unreacted components. It is preferable as it is less dangerous.

Phenolic resins include novolak type phenolic resins that require a curing agent and resol type phenolic resins that have self-curing properties, but when epoxy resin is used as a curing agent and cured, there are no reaction by-products, so the properties are stable. is preferable because it is easy to obtain.

Epoxy resins used in the present invention include bisphenol A type epoxy resin, tetrabromobisphenol A
Bisphenol A type epoxy resin such as type epoxy resin,
Phenol novolac type epoxy resins such as phenol novolac type epoxy resins, Talezol novolac type epoxy resins, brominated phenol novolac type epoxy resins, etc. Examples thereof include polyglycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids such as adipic acid, phthalic acid, and dimer acid.

The ratio of the novolac type phenol resin to the epoxy resin is preferably 20 to 400 parts by weight of the epoxy resin to 100 parts by weight of the novolac type phenol resin.

As curing accelerators, tertiary amines such as piperidine, triethanolamine, triethylamine, and lysine, or 2-methylimidazole, 2-ethylimidazole,
2-phenylimidazole, 4-methylimidazole,
Imidazoles such as 2-ethyl-4-methylimidazole are used.

The amount ratio of epoxy resin and curing accelerator is 1
The amount is 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, and if it is less than 0.05 parts by weight, curing will be slow, and if it is more than 5 parts by weight, the curing rate will be high. This is not preferable because it becomes difficult to control.

The ratio of the thermosetting resin component, which is a mixture of phenol resin and epoxy resin, to the radical polymerization reaction component varies depending on the required properties, but it is 10 to 1000 parts by weight of the radical polymerization reaction component to 100 parts by weight of the thermosetting resin component. be.

Examples of the radical polymerization initiator include azo radical polymerization initiators such as 2,2'-azobisisobutyronitrile and 1,1'-azobis(1-cyclohexanecarbonitrile);
Peroxide-based radical polymerization initiators such as dicumyl peroxide and di-t-butyl peroxide, and redox-based radical polymerization initiators such as persulfate-polyamine and organic halide-zero-valent transition metal systems are used. Moreover, two or more types of these radical polymerization initiators may be used. The amount of radical polymerization initiator added is 10% of the resin component.
It is preferably 0.05 to 15 parts by weight relative to 0 parts by weight.

If the amount of the radical polymerization initiator added is less than 0.05 parts by weight, radical polymerization will be difficult to proceed, and if more than 3415 parts by weight is used, the polymerization reaction rate will be high and control thereof will be difficult, which is not preferred.

Further, the filler used in the present invention is not particularly limited, but a combination of a scaly filler and a particulate filler is preferably used. The combination ratio is approximately 50
: It is preferable to set it as 50.

The amount of filler added is preferably 25 to 500 parts by weight per 100 parts by weight of the resin component.

Examples of scaly fillers include mica, scaly graphite, alumina flakes, silicon carbide flakes, steel flakes, aluminum flakes, nickel flakes, stainless steel flakes, glass flakes, etc., and the type, aspect ratio, etc. are selected depending on the application. do.

Particulate fillers include ferrite, iron powder, lead powder, copper powder, aluminum powder, glass beads, calcium carbonate, silica, alumina, graphite, magnesium carbonate, barium sulfate, barium carbonate, cork powder, glass balloons, etc. The type and particle size are selected depending on the purpose.

Specifically, the base materials used in the present invention include natural fiber cloths such as paper and cotton cloth, organic synthetic fiber cloths such as polyamide, polyester, polyvinyl alcohol, and acrylic, and inorganic fiber cloths such as glass, rock wool, and asbestos. Alternatively, these nonwoven fabrics, mats, etc. may be mentioned. Furthermore, in order to improve the permeability of the resin into the base material, it is desirable to use fibers that have been surface-treated.

Next, a method for manufacturing the vibration damping material of the present invention will be explained.

Each component of the resin composition for vibration damping material is thoroughly mixed to obtain a mixture. When this mixture has a low viscosity, it is impregnated or coated onto a continuously conveyed long base material, and when it has a high viscosity, it is coated or laminated in the form of a sheet. When laminating multiple base materials, the resin composition for damping material is coated, impregnated, or laminated in sheet form for each base material, and then the base materials with the obtained resin composition are laminated continuously. The laminated base material obtained in combination was
゜150~200' under pressure of 1~200kgf/cj
By continuously heating and pressurizing at C for 10 to 120 minutes, a long vibration damping material is obtained. In addition, when the base materials are not laminated, the resin composition for vibration damping material may be applied or laminated on one or both sides of the long base material that is continuously conveyed, or Impregnating from one or both sides of the material,
A long vibration damping material is obtained by heating and press-molding this as it is at 150 to 200° C. for 10 to 120 minutes under a pressure of 0.1 to 200 kgf/cd.

Resin compositions for vibration damping materials usually weigh 3 to 10 kg for the base material.
/nf is used.

Adhesives applied to damping materials or laminated in sheet form are:
Natural rubber, acrylic rubber, butyl rubber, chloroprene rubber, SIS (styrene-isoprene-styrene rubber)
, 5BS (styrene-butadiene-styrene rubber) and elastomers modified with these are used as main components. In addition, adhesives include natural rubber, nitrile rubber,
Urethane rubber, SBR (styrene-butadiene rubber),
Polyester resins, urea resins, melamine resins, phenol resins, epoxy resins, polyimide resins, cyanoacrylates, vinyl acetate resins, acrylic resins, polyamide resins, polyvinyl acetal resins, polyvinyl alcohol resins, and modified or combinations thereof are used. These pressure-sensitive adhesives or adhesives are applied in the form of emulsilane or solution to one or both sides of a continuously formed long vibration damping material, or are made into a sheet and applied to one or both sides of the long vibration damping material. By laminating them, the desired vibration damping material can be obtained.

When attaching vibration damping material, if the appropriate attachment site is clear in advance and it is not assumed that it will be attached or removed, it is preferable to apply an adhesive to the vibration damping material, but if the attachment site is not clear. If there is a high possibility that the device will be repeatedly attached and detached, or if it is expected that the device will be repeatedly attached and detached, it is preferable to use an adhesive coated device.

[Effect]

The damping material of the present invention exhibits good workability and stability during storage and transportation because the resin phase exhibits a damping function and the base material maintains rigidity.

In this way, since it is a composite material in which different materials perform their respective roles, it was possible to create a material that has a good overall balance. Furthermore, since the molded product obtained by molding the resin composition of the present invention is a composite polymer having an IPN structure, the applicable temperature range can be freely set by selecting the resin composition.

〔Example〕

Examples 1 to 3, Comparative Examples 1 to 3 (Synthesis of resin) 940 g of phenol, 560 g of 80% formaldehyde, 165 g of 37% formalin aqueous solution, and 2.7 g of oxalic acid were placed in a reaction vessel, and the temperature was gradually raised from room temperature. After emulsification, heating was continued for 3 hours at reflux temperature. Next, dehydration and concentration were performed under reduced pressure to remove by-produced water, unreacted formaldehyde, and phenol. In this way, a novolac type phenol resin having a softening point of 90°C was obtained.

(Manufacture of vibration damping material) 250 g of the above novolac type phenol resin and 250 g of bisphenol A type epoxy resin as thermosetting resin components.
g, 450 g of styrene and 50 g of ethylene glycol dimethacrylate are selected as radical polymerization reaction components,
These were thoroughly stirred at 60 to 100°C for about 1 hour. To this was added 500 g of mica as a scaly filler, 500 g of ferrite as a particulate filler, and 5 g of zinc stearate as a mold release agent, and kneaded for about 30 minutes. Finally, 10g of 2-ethyl-4methylimidazole (2E4MZ) as a curing accelerator and 10g of dicumyl peroxide (DCP) as a radical polymerization initiator were added, and the mixture was stirred and kneaded until uniformly dispersed. A resin composition A for vibration materials was obtained.

FIG. 1 is an overall explanatory diagram of an apparatus for continuously manufacturing a long vibration damping material.

Using the apparatus shown in FIG. 1, the resin composition A for the thermosetting vibration damping material 90 is supplied from the damping material resin composition mixing tank 2, and the vibration damping material coating apparatus 3 is used to supply the resin composition A for the thermosetting vibration damping material 90 per 1M of the base material. 6k
g on both sides of a continuously conveyed long glass cloth base material 1 whose surface has been treated with an aminosilane coupling agent, and three sheets are stacked by a superimposing device 4, and then heated and pressed into a press molding device. 5, under pressure of 1 kgf/cJ 1
Continuous heating and pressure molding was carried out at 70°C for 20 minutes. Subsequently, a toluene solution of butyl rubber supplied from the adhesive supply tank 6 is applied to one side of the long molded product obtained here using the adhesive coating device 7 so that the thickness of the butyl rubber layer becomes 1 mm, and the adhesive is directly bonded. The resin was dried in the agent drying device 8 at 120°C for 5 minutes, then at 170°C for 10 minutes, and the post-curing reaction of the resin was also progressed to achieve the desired thickness of 10mm.
A vibration damping material 9 having a length of 0 was obtained.

(Example 1) Styrene 450, the radical polymerization reaction component of Example 1
Example 1: g and 50 g of ethylene glycol dimethacrylate were replaced with 450 g of styrene and 200 g of polyethylene glycol dimethacrylate having 23 ethylene glycol units to obtain resin composition B for thermosetting vibration damping material.
A damping material was obtained in the same manner. (Example 2) The resin composition A for thermosetting vibration damping material of Example 1 was applied on both sides of a continuously conveyed long glass cloth whose surface was treated with an aminosilane coupling agent in the same manner as in Example 1. death,
The three sheets were molded as they were without stacking them under the same conditions as in Example 1, and a butyl rubber layer was subsequently provided in the same manner to obtain a damping material with a thickness of 3IIIffl. (Example 3) The resin composition A for thermosetting vibration damping material of Example 1 was introduced into a mold and cured at 170°C12O for minutes to obtain a vibration damping material with a thickness of 10 wm. A butyl rubber layer was provided on one side of the obtained damping material in the same manner as in Example 1 to obtain a damping material. (Comparative Example 1) Asphalt-based vibration damping material was layered on both sides of glass cloth, and three sheets were stacked to produce a load of 5 kgf/
A damping material with a thickness of 10 ma+ was obtained by heat-pressing molding at 100° C. for 2 minutes under a pressure of d. (Comparative example 2)
2 (Vibration damping performance evaluation method) The damping materials shown in Examples 1 to 3 were cut into appropriate sizes, and these and the damping materials shown in Comparative Example 1.2 were cut to a thickness of 1.5 mm.
It was attached to a 5 mm steel plate. In addition, asphalt-based vibration damping material was applied directly to a steel plate with a thickness of 1.5 mm to a thickness of 10flIf
iI to obtain a test piece. (Comparative Example 3) The steel plate surface of these test pieces was vibrated by the impulse flame method,
The logarithmic damping rate (damping performance evaluation index) was determined from the resonance frequency and half-width. The measurement temperature was the surface temperature of the steel plate.

Table 1 shows the vibration damping performance evaluation results, workability, and stability during storage and transportation.

3 [Effects of the Invention] As is clear from the results in Table 1, the vibration damping material obtained using the resin composition of the present invention exhibits an excellent vibration damping effect at temperatures from room temperature to 150°C, It has excellent workability and also has excellent stability during storage and transportation.

[Brief explanation of the drawing]

FIG. 1 is an overall explanatory diagram of an apparatus for continuously manufacturing a long vibration damping material. Explanation of symbols Base material 2 Resin mixing tank for damping material Resin coating device for damping material Layering device 5 Heat and pressure molding device Adhesive supply tank 7 Adhesive coating device Adhesive drying device 9 Damping material 5 11

Claims (1)

[Claims] 1. A resin composition for a thermosetting vibration damping material is coated or impregnated on a continuously conveyed long base material if the resin composition has a low viscosity; When the composition has a high viscosity, it is coated or laminated in the form of a sheet, and the resulting resin composition-coated base material is laminated singly or in multiple layers, and then the resin composition is continuously molded under heat and pressure. A method for producing a vibration damping material, which comprises allowing a curing reaction to proceed, and then continuously coating or laminating a pressure-sensitive adhesive or an adhesive on one or both sides of the obtained elongated molded product in the form of a sheet. 2. A resin composition for a thermosetting vibration damping material is obtained by adding a filler, a curing accelerator, and a radical polymerization initiator to a resin component consisting of a phenol resin, an epoxy resin, and a radical polymerization reaction component having radical polymerization ability. The method for producing a control material according to claim 1, which is a resin composition for a thermosetting vibration damping material. 3. Claim 2, wherein the radical polymerization reaction component contains at least one type of polyfunctional compound having difunctionality or more.
Method of manufacturing the vibration damping material described. 4. The method for producing a vibration damping material according to claim 2, wherein the filler is a combination of a scaly filler and a particulate filler. 5. The method for producing a vibration damping material according to claim 1, wherein the base material is made of a woven fabric or nonwoven fabric made of organic fibers or inorganic fibers, or a fiber entangled body obtained by processing organic fibers or inorganic fibers into a net shape.