JP2005119086A - Transparent damping laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent damping laminate having high damping properties, excellent in transparency and reduced in the lowering of transparency caused by deterioration with the elapse of time. <P>SOLUTION: This transparent damping laminate is constituted by laminating a plastic transparent sheet on at least one side of a transparent damping material composed of 100 pts.wt. of a thermoplastic resin being an acrylic resin or a chlorine-containing resin and 150-1,000 pts.wt. of a chlorinated paraffin wherein the content of chlorine is 20-75 wt.% and the average number of carbon atoms is 12-50. The absolute value of the difference between the SP value of chlorinated paraffin and the SP value of the plastic laminated to the transparent damping material of the plastic transparent sheet is 0.5 or above. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a housing structure such as a house, an apartment, an office building, various structures such as a highway, a viaduct, and a railroad track, various vehicles such as an automobile, a railcar, and a ship, and a home electric appliance,
A transparent damping laminate suitably used to reduce vibrations and noises generated in A equipment, etc., especially transparent materials that require transparency, such as transparent soundproof windows and transparent soundproof walls The present invention relates to a damping laminate.

Conventionally, the loss tangent (tan δ = E ″ / E ′) obtained by dividing the loss elastic modulus (E ″) by the storage elastic modulus (E ′) of the material has been used as a vibration damping index, and the loss tangent is large. It can be said that the material is excellent in vibration absorption. In general, when the value of the loss tangent (tan δ) exceeds 1, an excellent vibration damping material is obtained. However, further improvement in the vibration damping property is desired, and the loss tangent (tan δ)
) High material is desired.

Various materials have been proposed as the vibration damping material. For example, base polymer materials having polar side chains such as chlorinated polyethylene and nitrile butadiene rubber, chlorinated paraffin,
A highly damped material composition comprising a sulfenamide-based dielectric material, liquid rubber, and the like has been proposed (see, for example, Patent Document 1).
JP-A-11-80562

However, the attenuation material manufactured from the above high attenuation material composition has insufficient transparency and cannot achieve transparency with a haze value of 20, such as a transparent soundproof window or a transparent soundproof wall. It could not be used for applications requiring transparency.

Further, the vibration damping material having transparency includes, for example, a chlorine-containing thermoplastic resin having a chlorine content of 20 to 70% by weight, a chlorinated paraffin having a chlorine content of 30 to 70% by weight, and a rosin compound. A transparent vibration damping sheet made of the composition has been proposed (for example, see Patent Document 2).
.
JP 2001-337682 A

The transparent vibration damping sheet has a haze value of 1.7 to 3.5 and excellent transparency. However, weather resistance, heat resistance, etc. are insufficient, and there is a problem that transparency is drastically lowered when laminated on a plastic transparent plate such as polycarbonate and used outdoors for a long time or under high temperature conditions. It was.

An object of the present invention is to provide a transparent vibration damping laminate having high vibration damping properties, excellent transparency, and little decrease in transparency due to deterioration over time in view of the problems of the above-mentioned conventional vibration damping materials. is there.

The transparent vibration-damping laminate of the present invention is a transparent vibration-damping laminate in which a plastic transparent plate is adhered to at least one surface of a transparent vibration-damping material comprising a thermoplastic resin and chlorinated paraffin, The absolute value of the difference between the SP value of the plastic and the SP value of the plastic on the surface affixed to the transparent damping material of the plastic transparent plate is 0.5 or more.

The thermoplastic resin used in the present invention is not particularly limited as long as it is transparent and can be mixed with chlorinated paraffin, but is preferably excellent in weather resistance, and is preferably an acrylic resin and chlorine. Containing resins are preferred.

Examples of the acrylic resin include methyl (meth) acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl (meth) acrylate, isobutyl acrylate, sec-butyl acrylate, n-pentyl acrylate, and n-hexyl. Acrylate, cumyl acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-methylheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, 2-methyl Octyl (meth) acrylate, 2-ethylheptyl (meth) acrylate, n-decyl (meth) acrylate, 2-methylnonyl (meth) acrylate, 2-ethyloctyl (meth) acrylate, laur Examples include homopolymers and copolymers of alkyl (meth) acrylates such as ru (meth) acrylate and copolymers of these alkyl (meth) acrylates as main components and monomers copolymerizable with alkyl (meth) acrylates. These may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with the alkyl (meth) acrylate include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene and propylene; (meth) acrylic acid, maleic anhydride, acrylonitrile, styrene, And vinylidene chloride.

The acrylic resin may be, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di Di (meth) acrylates such as (meth) acrylate; Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate; penta Erystol tetra (meth) acrylate; dipentaerythrole hexa (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanate Di- or triallyl compounds such as isocyanurate; divinylbenzene, may be crosslinked with polyfunctional monomers divinyl compounds such as butadiene.

The chlorine-containing resin is preferably a thermoplastic resin having 20 to 70% by weight of chlorine in the side chain and a weight average molecular weight of 400,000 or more.

When the chlorine content in the side chain of the chlorine-containing resin is less than 20% by weight, the chlorine-containing resin is easily crystallized, so that the storage elastic modulus (E ′) increases and the loss tangent (tan δ)
) Becomes smaller and the vibration damping performance decreases.

On the other hand, if the chlorine content exceeds 70% by weight, the intermolecular force becomes too strong, the storage elastic modulus (E ′) increases, the loss tangent (tan δ) decreases, and the damping performance decreases. 2
It is preferably 0 to 70% by weight, more preferably 30 to 60% by weight.

If the weight-average molecular weight of the chlorine-containing resin is less than 400,000, it becomes difficult to self-hold the shape when molded as a vibration-damping material such as a sheet or film. preferable. The upper limit of the weight average molecular weight is not particularly recognized, but if it exceeds 10 million, the moldability deteriorates and it becomes difficult to produce a vibration damping material, and therefore it is preferably 10 million or less.

The chlorine-containing resin may be substituted with a substituent other than chlorine. Examples of the substituent other than chlorine include a cyano group, a hydroxyl group, an acetyl group, a methyl group, an ethyl group, a bromine group, and a fluorine group. The content of substituents other than chlorine is preferably 5% by weight or less because if the content is too large, vibration damping properties may be insufficient.

Examples of the chlorine-containing resin include chlorinated ethylene resins, vinyl chloride resins, chlorinated vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and chlorinated ethylene resins are preferably used.

The chlorinated paraffin used in the present invention is not particularly limited, but the chlorine content is 20 to 75% by weight in terms of the balance between vibration damping properties and transparency of the obtained vibration damping material, Chlorinated paraffin having an average carbon number of 12 to 50 is preferred.

The chlorine content of the chlorinated paraffin is more preferably 30 to 75% by weight because if it is too low or too high, compatibility with the thermoplastic resin is deteriorated and vibration damping is reduced.

When the average carbon number of the chlorinated paraffin is less than 12, when used outdoors, the chlorinated paraffin is likely to bleed or aggregate due to ultraviolet rays or the like, the transparency after weathering deterioration is lowered, and the average carbon number is 50. If it exceeds 1, the viscosity becomes too high and handling becomes difficult.
2-50 are preferable, More preferably, it is 25-35.

The above chlorinated paraffins may be used alone, differing in chlorine content or carbon number 2
More than one species of chlorinated paraffin may be used in combination.

The SP value of the chlorinated paraffin is not particularly limited. However, when the absolute value of the difference from the SP value of the thermoplastic resin is increased, the compatibility with the thermoplastic resin is decreased, and the vibration damping performance and transparency are decreased. Therefore, the absolute value of the difference between the SP value of chlorinated paraffin and the SP value of the thermoplastic resin is preferably 1.0 or less.

When the amount of chlorinated paraffin added to the thermoplastic resin decreases, the loss tangent (ta
nδ) is high and excellent vibration damping properties cannot be obtained. Conversely, when it is increased, the mechanical strength is low and it is difficult to self-hold the shape when formed as a vibration damping material such as a sheet or film. Therefore, the addition amount of chlorinated paraffin is 150 to 1000 with respect to 100 parts by weight of the thermoplastic resin.
A weight part is preferable, More preferably, it is 300-900 weight part.

For the purpose of improving the moldability, stability, vibration damping property, etc. within the range not impairing the effects of the present invention, for example, an organic tin stabilizer, a metal soap heat stabilizer, a phenol Antioxidants, hindered amine light stabilizers, ultraviolet absorbers such as benzophenone and triazole may be added.

Examples of the organotin stabilizer include dialkyl tin malate, dialkyl tin bis (monoalkyl malate), dibutyl tin malate polymer, dialkyl tin laurate, dialkyl tin mercapto, dialkyl tin bis (mercapto fatty acid ester), dialkyl tin. Examples thereof include sulfides, dioctyl tin malate polymers, and the like, and stabilizers other than tin mercapto stabilizers that are not very excellent in weather resistance are preferable. These may be used independently and 2 or more types may be used together.

Examples of the phenol-based antioxidant include pentaerythritol tetrakis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [ 3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] and the like. These may be used independently and 2 or more types may be used together.

Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and decanedioic acid (2,2,6,6-tetramethyl-1 (
And a reaction product of octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane. These may be used independently and 2 or more types may be used together.

The shape of the above-mentioned transparent vibration damping material is not particularly limited. Residential structures such as houses, condominiums, office buildings, various structures such as highways, viaducts, railway tracks, various vehicles such as automobiles, railway vehicles, ships, and households The shape may be any shape generally used in electrical equipment, OA equipment, and the like, and examples thereof include a sheet shape, a tape shape, a film shape, and a rod shape. Further, these damping materials may be not only a single layer but also a multilayer structure, or a structure partially used as long as the effects of the present invention are not impaired.

As a method for producing a transparent vibration damping material such as a sheet, tape, film, or rod from the thermoplastic resin and chlorinated paraffin, any conventionally known method may be employed. For example, extrusion molding, press Examples thereof include a molding method, a roll molding method, and an injection molding method.

The plastic transparent plate used in the present invention may be a transparent plastic plate,
The plastic on the surface attached to the transparent damping material of the plastic transparent plate has an SP value whose absolute value of the difference from the SP value of the chlorinated paraffin is 0.5 or more.

If the absolute value of the difference between the SP value of the surface of the plastic transparent plate and the transparent damping material of the plastic plate is less than the SP value of chlorinated paraffin, the chlorination of the damping material will depend on the molding conditions and long-term use. Since paraffin moves to a plastic transparent plate, transparency and physical properties deteriorate.
It is 0.5 or more, preferably 1.0 or more, and more preferably 2.0 or more. In addition, SP value means a solubility parameter.

Examples of the plastic whose absolute value of the difference from the SP value of the chlorinated paraffin is 0.5 or more include silicon resin and polyethylene terephthalate resin.

The plastic transparent plate may have a single-layer structure, a laminated structure in which two or more plastic transparent plates are laminated, and transparent plastic is laminated on the surface of a plastic transparent plate having different SP values. The structure may be different.

As the plastic transparent plate having different SP values, those having excellent transparency and weather resistance are preferable, and examples thereof include a polycarbonate resin plate, a vinyl chloride resin plate, and an acrylic resin plate.

Moreover, the thickness of the said plastic transparent board is not specifically limited, Although what is necessary is just to determine suitably by a use, it is 1-10 mm generally.

In the transparent vibration-damping laminate of the present invention, a plastic transparent plate is stuck on at least one surface of the transparent damping material, but the sticking method is not particularly limited, and any conventionally known sticking method is adopted. Well, for example, when sticking a plastic transparent plate on both sides of a transparent damping material shaped like a sheet, sandwiching the damping material sheet between two plastic transparent plates, while heating the resulting sandwich body, It is possible to apply a method in which air existing between the vibration damping material sheet and the plastic transparent plate is extracted using a vacuum bag or a roll, or laminated while being expelled.

The structure of the transparent vibration-damping laminate of the present invention is as described above, and is a transparent vibration-damping laminate in which a plastic transparent plate is attached to at least one surface of a transparent vibration-damping material made of a thermoplastic resin and chlorinated paraffin. In addition, since the absolute value of the difference between the SP value of the chlorinated paraffin and the SP value of the plastic on the surface of the transparent plastic plate is 0.5 or more, it has high vibration damping properties. In addition, it has excellent transparency and little deterioration in transparency due to deterioration over time.

In particular, when the thermoplastic resin is an acrylic resin or a chlorine-containing resin, the compatibility with the chlorinated paraffin is excellent, and the vibration damping property and transparency are excellent.

Therefore, the transparent vibration-damping laminate of the present invention has little deterioration with time particularly in transparency in order to reduce vibrations and noises generated in various structures and vehicles, as well as household electrical equipment and OA equipment. Can be suitably used for a member (for example, a transparent soundproof wall, a vehicle window, etc.).

Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples. In addition, this invention is not limited only to the following Example.

(Example 1)
Polymethylmethacrylate resin (Made by Mitsubishi Rayon Co., Ltd., trade name “Dynar BR-88
”, Mw = 480,000) 100 parts by weight, chlorinated paraffin (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name“ Empara 50 ”, SP value = 9.4) and tin-based heat stabilizer (Three-sharing machine synthesis) 27 parts by weight of a product name “STANN, RC-680B” manufactured by the company is supplied to a pressure kneader (“DS0.5-3GHB-E” manufactured by Moriyama Co., Ltd.) and kneaded at 100 ° C. for vibration damping materials A resin composition was obtained. The obtained resin composition for damping material was press-molded at 120 ° C. to obtain a transparent sheet-like damping material having a thickness of 1 mm.

The obtained transparent sheet-shaped vibration damping material was obtained by using two double-sided silicon hard-coated polycarbonate plates (manufactured by Teijin Chemicals Ltd., trade name “PC-7129”, SP value of silicon-coated layer = 7.
3) It was sandwiched between (50 mm × 50 mm, thickness 2 mm), and subjected to pressure bonding with a press machine (manufactured by Toho Machinery Co., Ltd.) for 5 minutes under the conditions of 120 ° C. and pressure 6.6 MPa to obtain a transparent vibration-damping laminate.

(Example 2)
Methyl methacrylate-butyl acrylate copolymer (manufactured by Kaneka Corporation)
A60 ”, Mw = 7,500,000) 100 parts by weight, chlorinated paraffin (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name“ Empara 50 ”, SP value = 9.4) 800 parts by weight and tin-based heat stabilizer (three 27 parts by weight of a shared machine synthesis company, trade name “STANN, RC-680B”) is supplied to a pressure kneader (manufactured by Moriyama, “DS0.5-3GHB-E”), kneaded at 100 ° C., and controlled. A resin composition for vibration material was obtained. The obtained resin composition for damping material was press-molded at 120 ° C. to obtain a transparent sheet-like damping material having a thickness of 1 mm.

The obtained transparent sheet-shaped vibration damping material was obtained by using two double-sided silicon hard-coated polycarbonate plates (manufactured by Teijin Chemicals Ltd., trade name “PC-7129”, silicon-coated layer SP value = 7.3).
) (50 mm × 50 mm, thickness 2 mm), 5 under the conditions of 120 ° C. and pressure 6.6 MPa.
Crimping was performed with a press machine (manufactured by Toho Machinery Co., Ltd.) for a minute to obtain a transparent vibration damping laminate.

(Example 3)
400 parts by weight of chlorinated ethylene resin (chlorinated ethylene resin prepared by post-chlorination of high-density ethylene resin by water suspension method, weight average molecular weight 500,000, chlorine content 45% by weight), chlorinated paraffin (Ajinomoto Fine) Product name “Empara 50”, SP value = 9.4) 80, manufactured by Techno
0 parts by weight and tin-based heat stabilizer (trade name “STANN, RC-680B”, manufactured by Sankyo Gosei Co., Ltd.)
) 27 parts by weight was supplied to a pressure kneader (manufactured by Moriyama Co., Ltd., “DS0.5-3GHB-E”) and kneaded at 100 ° C. to obtain a resin composition for a vibration damping material. The obtained resin composition for damping material was press-molded at 120 ° C. to obtain a transparent sheet-like damping material having a thickness of 1 mm.

The obtained transparent sheet-shaped vibration damping material was obtained by using two double-sided silicon hard-coated polycarbonate plates (manufactured by Teijin Chemicals Ltd., trade name “PC-7129”, silicon-coated layer SP value = 7.3).
) (50 mm × 50 mm, thickness 2 mm), 5 under the conditions of 120 ° C. and pressure 6.6 MPa.
Crimping was performed with a press machine (manufactured by Toho Machinery Co., Ltd.) for a minute to obtain a transparent vibration damping laminate.

(Comparative Example 1)
Instead of the double-sided silicon hard-coated polycarbonate plate, a polycarbonate plate (manufactured by Teijin Chemicals Ltd., trade name “PC-1111”, surface SP value = 9.8) was used in the same manner as in Example 2. As a result, a transparent damping laminate was obtained.

(Comparative Example 2)
Instead of double-sided silicon hard-coated polycarbonate plate, use single-sided methyl methacrylate resin-coated polycarbonate (manufactured by Teijin Chemicals Ltd., trade name “PC-8111”, SP value of methyl methacrylate resin layer = 9.5), A transparent damping laminate was obtained in the same manner as in Example 2 except that the methyl methacrylate resin layer was laminated so as to be in contact with the transparent sheet damping material.

Using the transparent sheet-shaped damping material obtained in the examples and comparative examples, the loss tangent (
tan δ) peak value) was measured, and using the transparent vibration-damping laminates obtained in the examples and comparative examples,
The haze value was measured by the following method, and the results are shown in Table 1.

(1) Loss tangent Using the viscoelasticity measuring device (Rheometric Scientific F.E., “RDA-II”), the transverse elastic modulus of the obtained transparent sheet-shaped damping material with a thickness of 1 mm (G ', G
The measurement conditions were measured at a measurement frequency of 50 Hz and a measurement temperature of −40 ° C. to 60 ° C. to obtain a tan δ peak value.

(2) Haze value The obtained transparent vibration-damping laminate is supplied to a metal weather weathering evaluation tester (manufactured by Daipla Wintes Co., Ltd.), BP temperature is 50 ° C., irradiation intensity is 48 mW / cm ² , no shower, 150 A weathering deterioration acceleration test was conducted under the conditions of taking out after continuous irradiation for a period of time.

The haze (%) of the transparent vibration damping laminate before and after the irradiation was measured with a haze meter (trade name “TC-H3P” manufactured by Nippon Denshoku Industries Co., Ltd.).

As can be seen from Table 1, in the examples of the present invention, it has an excellent loss tangent, has a small haze value, good transparency, and retains transparency even after weather resistance deterioration. On the other hand, in the comparative example, it can be seen that the transparency after weathering deterioration is significantly reduced.

Claims (4)

A transparent vibration-damping laminate in which a plastic transparent plate is attached to at least one surface of a transparent vibration-damping material made of a thermoplastic resin and chlorinated paraffin, and the SP value of the chlorinated paraffin and the transparency of the plastic transparent plate A transparent vibration-damping laminate, characterized in that the absolute value of the difference from the SP value of the plastic on the surface affixed to the damping material is 0.5 or more. The transparent vibration-damping laminate according to claim 1, comprising 150 to 1000 parts by weight of chlorinated paraffin with respect to 100 parts by weight of the thermoplastic resin. The transparent vibration damping laminate according to claim 1 or 2, wherein the chlorinated paraffin has a chlorine content of 20 to 75% by weight and an average carbon number of 12 to 50. The thermoplastic resin is an acrylic resin or a chlorine-containing resin,
2. The transparent vibration-damping laminate according to 2 or 3.