JPH0761696B2 - Vibration-damping and sound-insulating material with thermosetting adhesive - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vibration-damping and sound-insulating material with a thermosetting pressure-sensitive adhesive, which has tackiness at room temperature and can be cured without lowering the cohesive force of the adhesive during heat curing. .

II Conventional technology A sheet-shaped or plate-shaped vibration-damping and sound-insulating material with an adhesive is a two-pack type epoxy adhesive consisting of a gum sheet or a resin sheet, an acrylic ester pressure-sensitive adhesive or a rubber-based adhesive, and a main agent and a curing agent. This is to reduce the noise by applying an adhesive or the like and adhering it to a vibrating member of automobiles, industrial equipment, OA equipment and the like.

However, conventionally, the adhesive used has various drawbacks.

Acrylic ester-based pressure-sensitive adhesives have a problem in adhesion durability such as peeling and displacement when used on a wall or ceiling surface at high temperature. Further, in the case of a rubber-based adhesive, there are problems such as safety and health problems caused by solvents and poor workability. In the case of an epoxy adhesive, there are problems such as difficulty in mixing and stirring and coating, and poor workability.

III Object of the invention The object of the present invention is to solve the above-mentioned drawbacks, to have sufficient adhesive strength, durability, and heat resistance after curing, and to prevent the adhesive cohesive force from decreasing even during heating and curing. Provided is a vibration-damping and sound-insulating material with a thermosetting pressure-sensitive adhesive, which is free from the risk of peeling from the adherend even when used in a region where creep properties are required when uncured.

IV Configuration of the Invention The present invention is a vibration damping and sound insulating material having a plate-shaped body and an adhesive layer on the surface of the plate body, wherein the adhesive layer comprises an epoxy resin 10
Acrylonitrile-butadiene copolymer containing a carboxyl group 3 to 15 parts by weight and synthetic rubber 60 to 10 parts by weight based on 0 part by weight.
Provided is a vibration-damping and sound-insulating material with a thermosetting pressure-sensitive adhesive, which comprises 0 part by weight and 20 to 150 parts by weight of a terpene phenol resin.

The constitution of the present invention will be described in detail below.

The epoxy resin used in the present invention is a polycondensation product of bisphenols and epichlorohydrins, which uses amine, acid anhydride, boron trifluoride, etc. as a curing agent and reacts with an epoxy group or a hydroxyl group to form an intermolecular compound. It is a thermosetting resin that crosslinks.

Carboxyl group-containing acrylonitrile used in the present invention
The butadiene copolymer is a carboxyl group-modified acrylonitrile-butadiene copolymer polymer compound.

The synthetic rubber used in the present invention is an elastic body having rubber-like elasticity and may be a synthetic polymer compound. Butadiene rubber, styrene-butadiene rubber, isoprene rubber, ethylene-propylene rubber, butyl rubber, chloroprene rubber, acrylonitrile-butadiene rubber, that is, nitrile rubber, ucryl rubber, urethane rubber, silicone rubber, fluororubber, polysulfide rubber, polyether rubber, chlorosulfone Polyethylene, etc. can be used,
Particularly preferred are styrene-butadiene rubber, nitrile rubber, chloropyrene rubber, vinyl pyridine rubber, butyl rubber and polysulfide rubber. The above synthetic rubbers may be used alone or in combination of two or more.

The terpene phenol resin is a copolymer of terpenes and phenols. Terpenes are a general term for hydrocarbons represented by the general formula (C ₁₀ H ₁₆ ) _n , and are semiterpenes (n = 1/2),
Monoterpene (n = 1), Sesquiterpene (n = 3 /
2), diterpenes (n = 2), triterpenes (n =
3), carotene (n = 4), polyterpene (natural rubber,
Gutta-percha) etc. Phenols are a general term for organic compounds in which an OH group is directly bonded to a benzene nucleus. Phenol (carbolic acid) cresol, xylenol, p-phenylphenol, catechol, resorcin, hydroquinone,
There are pyrogallol and the like.

In particular, a copolymer of terpenes and bisphenol A represented by the following formula, A copolymer of α-pinene and bisphenol A is preferable.

The mixing ratio of the above epoxy resin, carboxyl group-containing acrylonitrile-butadiene copolymer, synthetic rubber, and terpene phenol resin is such that the content of the carboxyl group-containing acrylonitrile-butadiene copolymer is 3 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin. By weight, the content of synthetic rubber is 60 ~
100 parts by weight, 20 to 150 parts by weight of terpene phenol resin. If the amount of the carboxyl group-containing acrylonitrile-butadiene copolymer is less than 3 parts by weight, the adhesive performance is low and
If it exceeds the amount by weight, the storage stability decreases. 60 synthetic rubber
If it is less than 100 parts by weight, the cohesive force of the adhesive will decrease during heat curing, and if it exceeds 100 parts by weight, the adhesive performance will decrease. When the amount of the terpene phenol resin is less than 20 parts by weight, the adhesive strength when uncured is low, and when it exceeds 150 parts by weight, the adhesive performance is deteriorated.

The adhesive constituting the adhesive layer of the present invention is an epoxy resin,
Carboxyl group-containing acrylonitrile-butadiene copolymer, synthetic rubber, various known curing agents as necessary as thermosetting adhesives other than terpene phenol resin,
Fillers and additives can be added.

The method for producing the thermosetting pressure-sensitive adhesive may be any method, but an example is given below.

Epoxy resin, carboxyl group-containing acrylonitrile-
Predetermined amount of butadiene copolymer, synthetic rubber and other necessary fillers, additives, etc. are pressurized using a pressure kneader, etc.
Knead under heating, add a curing agent after cooling and mix well, and then mix this mixture with epoxy resin,
The thermosetting pressure-sensitive adhesive of the present invention is obtained by adding and mixing with a solvent such as a terpene phenol resin and methyl ethyl ketone.

The above-mentioned thermosetting adhesive is provided in layers on the vibration damping and sound insulating material to obtain the vibration damping and sound insulating material of the present invention.

Vibration-damping and sound-insulating material: Rubber-based vibration-damping and sound-insulating material such as natural rubber, synthetic rubber, tire reclaimed rubber, vinyl chloride, vinyl acetate, vinyl chloride / vinyl acetate copolymer, epoxy resin, unsaturated polyester resin, etc. System vibration damping and sound insulating material, asphalt, rubber asphalt, etc.
It is a sound insulation material such as lead, and the vibration damping and sound insulation material may be used alone or in combination. It may also be a blend of rubber and resin. Further, known fillers, mica, talc, etc., plasticizers, and additives may be added.

The method for producing the vibration damping and sound insulating material of the present invention may be any method, but one example is shown below.

After the adhesive is dried by a roll coater, etc., it is coated on the release paper 1 and dried in a drying oven at 60 ° C to 100 ° C as shown in Fig. 1, and then a plate shape such as a vibration damping and sound insulating material is applied. It is transferred to the body 3 to obtain the vibration damping and sound insulating material 10 with the thermosetting adhesive of the present invention.

At the time of execution, as shown in FIG. 2, the release paper 1 is peeled off and the thermosetting adhesive layer 2 is attached to the vibrating member 4 or the like such as a wall or a ceiling surface.
The surfaces are bonded and heat-cured at 130-180 ℃ for 20-40 minutes to be used as a vibration damping and sound insulating material.

V Example Hereinafter, a more specific description will be given with reference to Examples and Comparative Examples.

Example 1 60 parts by weight of Epicoat 828, 3 parts by weight of Nipol 1072, and 60 parts by weight of Nipol 1001 were added to a pressure kneader heated to 80 ° C. according to the formulation shown in Table 1 and mixed for 40 minutes. Cooled to 30-40 ° C. After cooling, 8 parts by weight of dicyandiamide and 4 parts by weight of Curezol C ₁₇ Z were added, and the mixture was stirred for 20 minutes and taken out from the kneader.

In a sealed chamber, 134 parts by weight of this composition, 40 parts by weight of ESAB-500, 20 parts by weight of YS Polystar 2130, methyl ethyl ketone.
800 parts by weight was added, and the mixture was mixed for 2 hours, then taken out from the closed chamber and used as an adhesive.

This composition was coated on a release paper with a coating amount of 100 g / m ² after drying with a roll coater, and then passed through a drying oven at 80 ° C for 3 minutes, and then a vibration damping and sound insulating material Hama Damper R -2 to obtain a vibration-damping and sound-insulating material with a thermosetting adhesive having tackiness according to the present invention.

The evaluation methods and results are shown in Table-3.

Epicoat 828 (Shell Chemical, bisphenol-glycidyl ether type epoxy resin with an epoxy equivalent of 180) Nipol 1001 (Nihon Zeon, NBR) Nipol 1072 (Nihon Zeon, carboxyl group modified NB)
R) Curezol C ₁₇ Z (Shikoku Kasei Co., Ltd., imidazole type latent curing agent) ESAB-500 (Sumitomo Chemical Co., Ltd. CTBN modified bisphenol-glycidyl ether type epoxy resin) YS Polystar 2130 (Yasuhara Yushi Kogyo terpene phenol copolymer) : Bisphenol A type) Hama Damper R-2 (Yokohama Rubber vibration damping and sound insulating material) (Example 2) Same as Example 1 Epicoat 828 70 parts by weight Nipol 1001 80 parts by weight Nipol 1072 5 parts by weight Dicyandiamide 8 parts by weight Curezol C ₁₇ Z 3 parts by weight ESAB-500 30 parts by weight YS Polystar 2130 80 parts by weight Methyl ethyl ketone 800 parts by weight After mixing and stirring, apply to release paper and dry.
A vibration-damping and sound-insulating material with a thermosetting adhesive, which was transferred to No. 2, was obtained.

Table 3 shows the evaluation results of the obtained vibration-damping and sound-insulating material with a thermosetting adhesive having tackiness.

(Example 3) Similar to Example 1, Epicoat 828 80 parts by weight Nipol 1001 80 parts by weight Nipol 1072 10 parts by weight Dicyandiamide 8 parts by weight Curezol C ₁₇ Z 3 parts by weight ESAB-500 20 parts by weight YS Polystar 2130 100 parts by weight Methyl ethyl ketone After 800 parts by weight were mixed and stirred, they were applied to a release paper and transferred to a Hamadamper R-2 to obtain a vibration-damping and sound-insulating material having a thermosetting adhesive and having adhesiveness.

Table 3 shows the evaluation results of the obtained vibration-damping and sound-insulating material with a thermosetting adhesive having tackiness.

(Example 4) As in Example 1 Epicoat 828 80 parts by weight Nipol 1001 100 parts by weight Nipol 1072 15 parts by weight Dicyandiamide 8 parts by weight Curezol C ₁₇ Z 3 parts by weight ESAB-500 20 parts by weight YS Polystar 2130 150 parts by weight Methyl ethyl ketone After 800 parts by weight were mixed and stirred, they were applied to a release paper and transferred to a Hamadamper R-2 to obtain a vibration-damping and sound-insulating material having a thermosetting adhesive and having adhesiveness.

Table 3 shows the evaluation results of the obtained vibration-damping and sound-insulating material with a thermosetting adhesive having tackiness.

(Comparative Example 1) Same as Example 1 Epicoat 828 70 parts by weight Nipol 1001 30 parts by weight Dicyandiamide 8 parts by weight Curezol C ₁₇ Z 3 parts by weight ESAB-500 30 parts by weight YS Polystar 2130 80 parts by weight Methyl ethyl ketone 800 parts by weight are mixed. After stirring, it was applied to a release paper and transferred to Hamadamper R-2 to obtain a vibration-damping and sound-insulating material having a thermosetting adhesive and having adhesiveness.

Table 3 shows the evaluation results of the obtained vibration-damping and sound-insulating material with a thermosetting adhesive having tackiness and thermosetting property. As is clear from Table 3, unlike Examples 1 to 4, Comparative Example 1 caused a displacement of the vibration damping and sound insulating material during curing.

(Comparative Example 2) 50 parts by weight of Epicoat 828 50 parts by weight of Epichant 1007 50 parts by weight ([Chemical Chemicals [epoxy equivalent 1750 bisphenol glycidyl ether type, solid type] epoxy resin) Dicyandiamide 8 parts by weight Curezol C ₁₇ Z 3 parts by weight YS Polyster 2130 (10 parts by weight) Methyl ethyl ketone (800 parts by weight) was added, mixed for 2 hours, applied on a release paper, and transferred to Hamadamper R-2 to obtain a vibration-damping and sound-insulating material with a thermosetting adhesive having adhesion.

Table 3 shows the evaluation results of the obtained vibration-damping and sound-insulating material with a thermosetting adhesive having tackiness. In Comparative Example, unlike in Examples 1 to 4, the adhesiveness was weak, so that the workability of application was poor, and the vibration-damping and sound-insulating material was displaced during curing.

(Comparative Example 3) A main component of a two-pack type epoxy adhesive and a curing agent were mixed, and the mixture was applied on a Hamadamper R-2 and evaluated. The evaluation results are shown in Table 3. Since the two-pack type epoxy adhesive must be mixed and applied before being applied, the workability is poor and there is a problem of stains on the adhesive surface.

The compositions of Comparative Examples 3 to 4 are shown in Table 2.

(Comparative Example 4) A rubber-based adhesive was applied to the adherend surface and the vibration-damping and sound-insulating material, dried and adhered. The evaluation results are shown in Table 3. The rubber-based adhesive needs to be applied to the adhesive surface and dried before use, which is inferior in workability and uses a solvent, which is not preferable in terms of safety and hygiene.

(Comparative Example 5) Acrylic ester-based pressure-sensitive adhesives are most used as adhesives for vibration-damping and sound-insulating materials, and since they are adhered by adhesion, they have advantages such as good workability, but when hot (60 to 130 ° C) However, when used on a wall surface or a ceiling surface, there was a defect that adhesion was weak, creeping, slippage and peeling were likely to occur.

Evaluation method (1) 90 ° peeling (23 ° C) adhesive strength The pressure-sensitive adhesives of Examples and Comparative Examples and vibration-damping and sound-insulating materials with adhesives were adhered to a stainless steel plate (SUS 304), heated at 140 ° C, and then measured. A 90 ° peel test was performed at a temperature of 23 ° C.

(2) 90 ° peeling (80 ° C) adhesive strength The test was conducted in the same manner as in (1), but at a measuring temperature of 80 ° C.

(3) Peelability from the ceiling surface The pressure-sensitive adhesive and vibration-damping and sound-insulating material with adhesive of Examples and Comparative Examples were adhered to a stainless steel plate (SUS 304), heated and cured at 140 ° C, then held in a horizontal position, and measured at a temperature of 25 mm sample width at 80 ° C
Attach a weight (70g) to one end of the peeling length after 5 hours (mm)
Was measured.

(4) Adhesion workability As for the adhesion workability when uncured, whether the pressure-sensitive adhesive or the vibration-damping and sound-insulating material with an adhesive of Examples and Comparative Examples can be applied immediately after application (⊚), or not (cannot be handled in line, X) was evaluated.

(5) Creep test at the time of curing In a state where the pressure-sensitive adhesive and the vibration-damping and sound-insulating material with adhesive of Examples and Comparative Examples were adhered to a stainless steel plate (SUS 304) and made vertical
A creep test was performed at 140 ° C. during heat curing.

The evaluation was ⊚: no deviation of the vibration damping and sound insulating material during curing, ×: deviation of 1 mm or more. Comparative Examples 3 to 5 were not thermosetting and were not measured.

(6) Work environment Hygiene The work environment was evaluated as “Poor” when the work environment was a solvent-free environment, and “Excellent” when there was no such situation.

VI Effect of the invention The vibration damping and sound insulating material of the present invention has an epoxy resin, a carboxyl group-containing acrylonitrile-butadiene copolymer, synthetic rubber and a terpene phenol resin in a predetermined ratio, and has sufficient adhesive strength and durability after curing. In addition to heat resistance and heat resistance, it has a thermosetting adhesive layer that has excellent creep characteristics without reducing the cohesive strength of the adhesive when it is uncured, so the following curing There is.

1. When applied to vibrating members, etc., it can be easily installed by adhesion and has excellent workability.

2. Since it can be cured without softening during heat curing, the vibration and sound insulating material will not shift.

3. 130 ~ 180 ℃ × 20 ~ 40 minutes to cure and the vibration damping sound insulating material adheres, even when used at high temperature (60 ~ 130 ℃) on the wall or ceiling,
Has excellent durability without causing displacement or peeling.

4. Since it is solvent-free, it is excellent for safety and hygiene.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating a vibration damping and sound insulating material with a thermosetting pressure sensitive adhesive according to the present invention. FIG. 2 is a cross-sectional view for explaining the time when the present invention is implemented. Explanation of code 1 …… Release paper 2 …… Thermosetting adhesive layer 3 …… Plate 4 …… Vibration member 10 …… Vibration damping and sound insulation material with thermosetting adhesive

Claims (1)

[Claims] 1. A vibration damping and sound insulating material having a plate-shaped body and an adhesive layer on the surface of the plate-shaped body, wherein the adhesive layer is an epoxy resin.
Carboxyl group-containing acrylonitrile-butadiene copolymer 3 to 15 parts by weight and synthetic rubber 60 to 100 parts by weight
A vibration-damping and sound-insulating material with a thermosetting adhesive, which comprises 100 parts by weight and 20 to 150 parts by weight of a terpene phenol resin.