JP3016603B2 - Damping thin leaf - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vibration-damping thin leaf which is attached to a vibration generator to reduce vibration and noise. More specifically, the present invention provides a vibration-damping thin sheet having a pressure-sensitive adhesive layer containing a specific amount of a specific silicone-based copolymer and a specific amount of a diorganosiloxane, and having excellent vibration-damping properties in a relatively high temperature range. About.

[0002]

2. Description of the Related Art In recent years, vehicles such as automobiles, railways, and aircraft, office equipment, information equipment, electrical products, floors and roofs of buildings,
Vibration and noise of stairs and walls have become a problem, and many damping materials have been proposed as countermeasures.

As such a vibration damping material, acrylic adhesive material having viscoelasticity between two steel plates composite vibration damping steel plate or a three-layer structure laminated on one surface of the constraining layer such as a metal foil Is a two-layered sheet coated with an adhesive, a butyl rubber-based adhesive, etc., and is known as a vibration damping sheet that can reduce vibration and noise by post-processing such as being attached to a vibration generator. An object of the present invention is to provide an excellent vibration-damping thin leaf body capable of easily exerting the vibration-damping property by the latter post-processing.

[0004] With respect to the vibration damping sheet of such a two-layer structure, for example, JP-A-1-69336, and "pressure sensitive resistance vibration damping composition layer on the sheet (A), the layer A vibration-damping adhesive sheet having a two-layer structure with a restraining plate (B) for bonding and restraining and having a concavo-convex pattern on the surface of the (A) layer opposite to the (B) plate is disclosed. It is recommended to use rubber-based, acrylic-based or rubber-acrylic-based layers.

However, this proposal, as in the present invention, not or suggest anything like describe the use of pressure-sensitive adhesive layer formulated as a main component a specific silicone-based pressure-sensitive adhesive, thus such Of course, the special effect of using a special pressure-sensitive adhesive layer, that is, the excellent effect of having extremely excellent vibration damping properties and maintaining the vibration damping properties in a relatively high temperature range, is naturally required. Not disclosed at all. Moreover, as in this proposal, the vibration-damping pressure-sensitive adhesive sheet "having a concavo-convex pattern on the surface of the (A) layer opposite to the plate (B)" is complicated to manufacture,
The resulting vibration-damping adhesive sheet is also difficult to handle like a normal pressure-sensitive adhesive tape, such as being rolled up,
There are also problems with storage and transportation.

Further, in JP-A-63-69850, "a) -40 ° C. elastomer having the following glass transition point (A) 15 to 70 wt%, b) a glass transition temperature of -40 to 40 ° C. At least one selected from the group consisting of an elastomer (B) having a pour point, a tackifying resin (C) having a pour point or a softening point of -40 to 40 ° C, and a plasticizer (D) having a pour point of -40 to 40 ° C.
15-70% by weight of a seed, c) a tackifier resin having a softening point of 60 ° C. or more (E) 15-70% by weight.

[0007] However, this document does not disclose the use of a silicone-based pressure-sensitive adhesive at all.
Even if a damping sheet is made using this damping material composition,
The balance of the adhesive force, tackiness and cohesive force (holding force) of the pressure-sensitive adhesive layer is not always sufficient, and particularly when used at a high temperature, the attached vibration damping sheet may slip off, and may be rolled, for example. It has been found that when such a vibration damping sheet is stored at a high temperature such as in summer, the pressure-sensitive adhesive may protrude from the end face of the sheet.

[0008]

SUMMARY OF THE INVENTION The present inventors can effectively reduce vibration and noise by post-processing such as sticking to various vibration generators, and exhibit excellent vibration damping properties. As a result of conducting research to obtain a vibration-damping thin body that can be used, a pressure-sensitive adhesive layer containing a specific silicone-based adhesive is used as the pressure-sensitive adhesive layer of the vibration-damping thin body. As a result, the inventors have found that the above-described problems of the conventional vibration damping sheet can be solved, and have completed the present invention. That is, the present invention provides a relatively high temperature range (for example, 40 to
(120 ° C.) to develop a vibration-damping thin leaf having excellent vibration-damping properties.

[0009]

According to the present invention, there is provided a vibration-damping thin sheet having a pressure-sensitive adhesive layer on at least one surface of a constraining layer, wherein the pressure-sensitive adhesive layer is a main component. SiO ₂ units and R ₃ SiO _0.5 (wherein a, R represents may be the same or different, a lower alkyl group, lower alkenyl group, any group selected from among phenyl groups, among all the groups Is a lower alkyl group), and 30 to 95 parts by weight of a copolymer having a molar ratio to a unit of 1: 0.4 to 1: 1 and diorganopolysiloxane (where the organo group is a lower alkyl group and a lower alkyl group). alkenyl group is any group selected from among phenyl groups) 70 to 5 Ri do from the weight part, solved by the damping resistance thin material comprising a silicon-based pressure-sensitive adhesive containing no filler substantially can do.

[0010] Hereinafter, the present invention will be described in detail. Of the present invention
The vibration-damping thin body is sensitive to at least one surface of
Having a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer
Is, as described above, SiO 2_TwoUnit and R_ThreeSiO_0.5unit
(Wherein R may be the same or different, and is a methyl group
Any lower alkyl such as lower alkyl or vinylNil
Group, any group selected from phenyl groups, all groups
75% of the numbers are lower alkyl groups)
Is a copolymer having a ratio of 1: 0.4 to 1: 1
Parts, preferably 40 to 93 parts by weight, of the diorganopolicy.
Loxane (organo group is lower alkyl such as methyl group)
Group, lower alkenyl group such as vinyl group, and phenyl group
70 to 5 parts by weight, preferably
Or silicone adhesive consisting of 60 to 7 parts by weight.
Include as minutes.

[0011] As such a silicon-based adhesive, for example, manufactured by Shin-Etsu Chemical Co. (Ltd.) KR-120, KR-130 , K
R-108-60, SH-4280, X-40-3004A, S manufactured by Toray Dow Corning Silicone Co., Ltd.
D-4560, SD-4570, SD-4580, YR-3286, XR37-A05 manufactured by Toshiba Silicone Co., Ltd.
A commercially available product such as 37 can be suitably used.

The preferred silicone-based pressure-sensitive adhesive for use in the present invention has a loss tangent (tan δ) of its dynamic viscoelasticity.
Is 20 ° C. or higher, preferably 25 ° C.
The above are preferred because they exhibit excellent high-temperature damping properties.

[0013] pressure-sensitive adhesive layer in the damping property thin material of the present invention, in order to improve the agglutination force, the silicon-based adhesive, an organic peroxide, an organic tin compound, an organic carboxylic acid metal salt, It is preferable to crosslink with a crosslinking catalyst such as a sulfur vulcanizing agent, an amine compound, an inorganic acid, an organic acid, and a platinum compound.

[0014] As the organic peroxides, e.g., benzoyl peroxide, lauroyl peroxide, Cap Roy peroxide, di -i- propyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t- butyl peroxy Pi Bareto, 2,4-dichloro - can be mentioned benzoyl peroxide and the like.

Examples of the organic tin compounds, for example, dibutyltin diacetate, dibutyltin dilaurate, and the like can be illustrated dibutyltin dioctoate, as the organic carboxylic acid metal salts, such as tin naphthenate, tin oleate, lead octoate, zinc Octoate, zinc naphthenate and the like can be mentioned.

[0016] As the sulfur vulcanizing agent, for example, sulfur, tetramethylthiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and di-pentamethylene thiuram tetrasulfide can be exemplified.

[0017] As the amine compound, for example, triethylenediamine, 2-methyl-4-cyano-ethylimidazole, dibutylamine-2-ethylhexoate,
N- (3-trimethoxysilanopropyl) ethylenediamine and the like can be exemplified.

[0018] The inorganic acids are, for example, sulfuric, hydrochloric, nitric acid, phosphoric acid, and as the organic acids, e.g., benzoic acid, phthalic acid anhydride, such as p-toluenesulfonic acid can be exemplified.

Furthermore, as the platinum compound, for example, platinum black, chloroplatinic acid, platinum tetrachloride, platinum alcohol compounds, platinum olefin complexes, platinum aldehyde complexes, platinum ketone complexes,
Platinum methyl vinyl siloxane complex and the like can be mentioned.

[0020] Of these crosslinking catalysts, the use of organic peroxides and platinum compounds for reasons such as the size of the pot life of the length and cross-linking density of the pressure-sensitive adhesive composition used when pressure-sensitive adhesive layer formation is preferred.

The amount of the crosslinking catalyst used is generally from 0 to 10 based on 100 parts by weight of the silicone-based pressure-sensitive adhesive in total.
Parts by weight, preferably about 0.5 to 5 parts by weight. If the amount of the cross-linking agent used is not more than this upper limit, the pot life of the pressure-sensitive adhesive composition used is preferably long,
It preferred because excellent agglutination force equal to or more than parts by weight is obtained.

The pressure-sensitive adhesive layer in the vibration-damping thin sheet of the present invention may further comprise, if necessary, for example, a coumarone-indene resin, a terpene-phenol resin, a pt-butylphenol-acetylene resin, a phenol-formaldehyde resin. And a tackifying resin such as a terpene resin, a xylene / formaldehyde resin, a petroleum hydrocarbon resin, a hydrogenated hydrocarbon resin, a rosin derivative, and a turpentine resin. The addition amount of these resins is, for example, from 0 to 60 with respect to 100 parts by weight of the silicone-based pressure-sensitive adhesive.
The amount is preferably about 0 to 40 parts by weight, particularly preferably about 0 to 40 parts by weight.

In addition to the above, the pressure-sensitive adhesive layer of the present invention comprises
A plasticizer such as a phthalic acid ester such as dioctyl phthalate, a phosphate ester such as tricresyl phosphate, or a process oil, if necessary .
Organic coloring agent such as a full talo cyanine blue; ultraviolet absorbers; known additives such as preservatives may be added.

As described above, the pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer used in the present invention is preferably prepared by dissolving, for example, a silicon-based pressure-sensitive adhesive and a crosslinking agent in an organic solvent such as toluene and xylene. In addition, if necessary, a tackifying resin, a plasticizer, a colorant , and the like can be added and mixed to produce the composition.

The vibration damping property thin material of the present invention, the pressure sensitive adhesive composition as described above, on at least one surface of suitable constraining layer selected depending on the application, for example a roll coater,
After directly applying according to a generally known method such as a knife coater, drying, and heating or leaving at room temperature for crosslinking as required, a release material is placed on the formed pressure-sensitive adhesive layer, and And can be created by a method such as winding or cutting. Alternatively, the pressure-sensitive adhesive composition can be applied to a release material by a similar method, dried, and then bonded to a constraining layer. The thickness of the pressure-sensitive adhesive layer is generally about 10 to 200 μm, preferably about 2 to 200 μm.
The thickness is preferably about 0 to 150 μm.

[0026] Examples of the constraining layer of the above, for example, iron, steel,
Aluminum, nickel, chromium, cobalt, stainless steel, zinc-treated steel sheet, copper-plated steel sheet, metal or metal alloy foil such as copper and brass; for example, polycarbonate, polystyrene, vinyl chloride, polyethylene terephthalate, polyamide, thermoplastic polyurethane, petroleum -Based hydrocarbon resin, cumarone-based resin, rosin derivative, natural resin, thermoplastic resin film or sheet having a softening point of 60 ° C. or more such as natural asphalt; for example, phenol resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin And thermosetting resin sheets such as urethane resin; inorganic sheets such as glass and ceramic; and paper such as cardboard and corrugated cardboard. Of these, metal or metal alloy foils, especially stainless steel, copper,
The use of foils such as aluminum and copper plated steel sheets is preferred.

[0027] The thickness of the constraining layer is generally about 10~200μ
m, preferably about 25 to 100 μm.

The term "lamella" used in the present invention means, for example, a film, a sheet, a tape, a strip, a ribbon, a thin plate or the like in comparison with the dimension in the length and / or width direction. This is a term indicating a shape whose dimension in the thickness direction is extremely small.

The vibration damping property thin material of the present invention, for example, only attaching automobile, railway vehicle, a vehicle such as an aircraft, information equipment, electrical products, building floors, roofs, walls, a vibration generating body such as stairs Easily and relatively high temperature range (for example, 40 to
(120 ° C.), the generation of vibration and noise can be effectively suppressed.

[0030]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to these Examples.

The method for preparing the pressure-sensitive adhesive sheet for testing the vibration-damping thin leaf of the present invention, the method for measuring the tack, the adhesive force and the holding force, and the method for measuring the vibration-damping property are as follows. (1) Method of preparing pressure-sensitive adhesive sheet for test A pressure-sensitive adhesive composition solution is dried on a stainless steel foil having a thickness of 50 μm, and the thickness of the pressure-sensitive adhesive layer when dried becomes the value shown in Table 1. After drying at 80 ° C. for 5 minutes in a hot air circulating drier and then cross-linking at 150 ° C. for 10 minutes, a release material is placed on the resulting pressure-sensitive adhesive layer and tested for testing. A pressure-bonded sheet was obtained. (2) Measurement of tack According to JIS Z 0237 method, the test pressure-sensitive adhesive sheet (100 mm in length of the test piece) prepared in the preceding paragraph (1) was attached to a slope having an inclination angle of 30 °. Up slope 10
A steel ball having a diameter of x 2/32 inches is rolled from the position of 0 mm, and is indicated by the diameter x of the largest diameter ball that stops on the sample. (3) Adhesion test A test piece cut out from the test pressure-sensitive adhesive sheet prepared in (1) above was cut into a SUS304 stainless steel plate polished with # 280 water-resistant abrasive paper specified in JIS Z 0237. And after 1 hour, 23 ° C., 65% RH, peeling speed 300 mm / min.
The peel strength (g / 25 mm) is measured under the following conditions. (4) the same stainless steel plate as that used in the pre-measurement (3) section of the holding force, the front (1) test piece cut from the pressure-sensitive adhesive sheet test created in the section, the contact Chakumenseki 25 × 25 mm ² , and pressed back and forth with a 2 kg roller once. This was subjected to 1kg static load under 80 ° C. atmosphere sample to measure the time until the load falls. (5) Measurement of vibration damping property The test pressure-sensitive adhesive sheet prepared in the preceding paragraph (1) was attached to a 0.5 mm-thick zinc-treated steel sheet, and this was used as a test piece at a frequency of 200 Hz by a resonance method. Is measured at each temperature. The results are shown in FIGS. In the damping thin sheet of the present invention, the loss coefficient (η)
Is preferably 0.04 or more in a temperature range of 40 to 120 ° C.

EXAMPLES AND COMPARATIVE EXAMPLES A base pressure-sensitive adhesive composition was prepared by blending the main ingredient and the crosslinking catalyst shown in Table 1 with each other. Table 1 shows the measurement results of the dynamic viscoelasticity. The main ingredients used are as follows. (1) KR-120 Silicone pressure-sensitive adhesive manufactured by Shin-Etsu Chemical Co., Ltd. (2) KR-130 (3) X-40-3004 (4) SH-4280 Dow Corning Toray Silicone ( (5) SP-001 Acrylic pressure-sensitive adhesive manufactured by Nippon Carbide Industry Co., Ltd. (6) SP-002

[0033]

[Table 1]

[Brief description of the drawings]

FIG. Damping thin leaf bodies of Examples 1 to 3 which are embodiments of the present invention
Graph showing the vibration damping test results of FIG.

FIG. 2 Damping thin leafs of Examples 4 to 7 which are embodiments of the present invention
It is a graph which shows the damping test result of a.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kenichi Masuhara ▲ Taka ▼ Ichikawa City, Chiba Prefecture 1 at Nishin Steel Co., Ltd. New Materials Research Laboratory (72) Inventor Ryoichi Kato Ichikawa City, Chiba Prefecture ▲ Taka ▼ 7 in Nishinshin Steel Co., Ltd., New Materials Research Laboratory (72) Inventor Hiroshi Enya 7-1, Takatani Shinmachi, Ichikawa-shi, Chiba Pref. 7 Nisshin Steel Co., Ltd., New Materials Research Laboratory, 7 Takayashinmachi, Ichikawa City (56) References JP-A-1-69336 (JP, A) JP-A-63-297458 (JP, A) (58) (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 F16F 15/00-15/36

Claims (2)

(57) [Claims] 1. A damping thin sheet having a pressure-sensitive adhesive layer on at least one surface of a constraining layer, wherein the pressure-sensitive adhesive layer has SiO ₂ units and R ₃ SiO _0.5 (wherein R
May be the same or different and represent an arbitrary group selected from a lower alkyl group, a lower alkenyl group and a phenyl group, and at least 75% of all groups are lower alkyl groups. Molar ratio of 1: 0.4 to 1: 1
30 to 95 parts by weight of a copolymer represented by the following formula: 70 and a diorganopolysiloxane (the organo group is an arbitrary group selected from a lower alkyl group, a lower alkenyl group and a phenyl group) 70
Ri Do and a 5 parts by weight, vibration-damping properties thin material comprising silicon <br/> con pressure-sensitive adhesive containing no filler substantially. 2. The pressure-sensitive adhesive layer has a loss coefficient at a frequency of 200 Hz of 0.04 at a temperature of 40 to 120 ° C.
The damping thin leaf body according to claim 1, which is the above.