JPH0450264A - Resin composition for vibration-damping material and production of vibration-damping material - Google Patents

Abstract

PURPOSE:To provide a resin composition for vibration-damping material, containing a thermoplastic resin and a monofunctional polymerizable monomer as essential components and capable of forming a vibration-damping material having high performance by applying the resin to a metal plate, eliminating the fluidity of the resin by heating, laminating the plates and hot-pressing the laminate. CONSTITUTION:The objective resin composition for vibration-damping material is composed of (A) a mixture of (A1) a thermoplastic resin (preferably vinyl chloride resin) and (A2) a monofunctional polymerizable monomer [preferably a (meth)acrylate modified with epsilon-caprolactam] at a weight ratio of 80/20 to 20/80 (preferably 70/30 to 30/70) and optionally (A3) a polyfunctional polymerizable monomer and/or (A4) a polymerization initiator (e.g. t-butyl peroxybenzoate) and is produced by compounding the component A to a mixture containing B and other additives and defoaming the product. A vibration- damping material can be produced by applying the above composition (B) to a metal plate, eliminating the fluidity with heat, laminating plural metal plates and hot-pressing the laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition for a vibration damping material and a method for producing a vibration damping material using the composition.

[Prior art] Vibration damping materials are materials that have the function of suppressing vibrations by converting vibration energy into heat energy and absorbing it. Conventionally, epoxy resins and urethane resins have been proposed as thermosetting resins for vibration damping materials. ing.

[Problems to be Solved by the Invention] However, when manufacturing vibration damping materials using these thermosetting resins, the working time is limited by the pot life of the resin, and once mixed, it cannot be stored and the yield is high. There were some problems, such as: . Furthermore, in the case of a so-called sandwich-type metal plate in which a resin is sandwiched between two metal plates, there is a problem that the viscosity of the resin decreases and flows out from between the two metal plates during pressure bonding and heating.

[Means for Solving the Problems] The present inventors have diligently studied a resin composition for thermosetting vibration damping materials that solves these problems, and a method for producing vibration damping materials using the resin. invention has been achieved.

That is, the present invention provides a control system consisting of (A) a thermoplastic resin, (B) a monofunctional polymerizable monomer, and, if necessary, a polyfunctional polymerizable monomer (C) and/or (D) a polymerization initiator. A resin composition for vibration materials, a vibration damping material using the resin composition, and a method for producing the same.

The thermoplastic resin (A) in the present invention is not particularly limited, but includes, for example, vinyl chloride resin and ABS.

Examples include MBS, NBRl polyethylene, polypropylene, and nylon. Preferably, vinyl chloride resin and vinyl chloride resin and other thermoplastic resins such as A
BS, MBSl PMMA, polycaprolactone,
It is a mixture with chlorinated polyolefin.

Vinyl chloride resins include vinyl chloride homopolymers, or vinyl chloride and other vinyl monomers, such as unsaturated vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, and vinyl propionate. Examples include copolymers with monomers and post-chlorinated products of these polymers. Particularly preferred are vinyl chloride homocopolymers and copolymers with a vinyl chloride content of 70% by weight or more.

Examples of the monofunctional polymerizable monomer (B) in the present invention include linear, branched, and cycloaliphatic alcohols having 6 to 20 carbon atoms (hexanol, n-octatool, 2-ethylhexanol, decyl alcohol, lauryl alcohol). ,
cyclohexanol, methylcyclohexanol, norbornyl alcohol, inbornyl alcohol, dicyclopentanyl alcohol, etc.), phenol, alkyl (01-C2-alkyl group) phenol, etc., and their alkylene oxides (ethylene oxide,
propylene oxide, etc.) adducts (hereinafter abbreviated as AOA) [(meth)acrylate refers to acrylate and methacrylate.

Similarly, lactone (such as ε-caprolactone) adducts of AOA of (meth)acrylic acid [hereinafter referred to as lactone-modified (meth)acrylates], aliphatic carboxylic acids having 1 to 20 carbon atoms, substituted or unsubstituted AOA (meth)acrylates of carboxylic acids such as benzoic acid, styrene, α
- Examples include methylstyrene and vinyl carboxylate.

Preferred are (meth)acrylates of alkylphenol AOA having an alkyl group having 1 to 20 carbon atoms and ε-caprolactone-modified (meth)acrylates.

In the present invention, the weight ratio of (A) and (B) is not particularly limited, but is usually 80/20 to 20/80, preferably 70/30 to 30/70.

If (A) is less than 20 or more than 80, the desired vibration damping performance cannot be obtained.

In the present invention, part of (B) can be replaced with (C) a polyfunctional polymerizable monomer if necessary.

(C,) and 7 are, for example, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, bisphenol A1 bisphenol F1 hydrogenated bisphenol A1 hydrogenated bisphenol F1 glycerin, Glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and poly(meth)acrylic acid esters of these AOAs, prepolymers obtained from these AOAs and polyisocyanates, and hydroxyl group-containing (meth)acrylates such as hydroxyethyl (meth)acrylate ) acrylate and so-called urethane (meth)acrylate.

The polyisocyanates used to produce the above-mentioned urethane (meth)acrylate include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in the NGO group), aliphatic polyisocyanates having 2 to 18 carbon atoms, carbon Number 4~
15 alicyclic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates (modified with urethane groups, carbodiimide groups, allophanate groups, urea groups, incyanurate groups, oxazoline groups) etc.) and urethane prepolymers made of these polyisocyanates and active hydrogen-containing compounds.

The weight ratio of (B) and (C) is usually 10010 to 5/
95, preferably 80/20 to 10/90.

In the present invention, the above (B) or (B) and (
In addition to C), a polymerizable monomer containing a polar group can be added in order to impart adhesiveness to the metal plate.

The polymerizable monomer containing a polar group in the present invention is not particularly limited, and includes a carboxyl group, an amino group, a phosphoric acid group (>
Those containing at least one polar group such as P-OH), sulfonic acid group (-8OaH), and salts thereof can be used.

Examples of polymerizable monomers containing a carboxyl group include (meth)acrylic acid, esterified products of hydroxyalkyl (meth)acrylates and polybasic acids and/or their anhydrides [co/monophosphoric acid mono( meth)acrylate, isophthalic acid mono(meth)acrylate, etc.]
can be given. Examples of polymerizable monomers containing amino groups include dialkyl (the number of carbon atoms in the alkyl group is usually 1 to 4) aminoalkyl (the number of carbon atoms in the alkyl group is usually 2 to 4) (meth)acrylate, etc. can be given. In addition, as a polymerizable monomer containing a phosphoric acid group, E
O-modified phosphoric acid mono(meth)acrylate [(HO) 2-P-OCH2CH*0-C-C”CH
Examples of a and R include a hydrogen atom or a methyl group, and EO-modified phosphoric acid di(meth)acrylate. Examples of the polymerizable monomer containing a sulfonic acid group include vinylsulfonic acid and (meth)acrylamidopropanesulfonic acid.

Preferably, it is a polymerizable monomer containing a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

The amount of the polymerizable monomer containing a polar group added is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total of (B) and (C).

In the present invention, a polymerization initiator (D) can be added if necessary. Examples of the polymerization initiator include benzoyl peroxide, dicumyl peroxide, t-
Examples include butyl peroxybenzony l-1t-butylperoxy 2-ethylhexanoate, di-t-butyl peroxide, methyl ethyl ketone peroxide, and azobisisobutyronitrile. The amount added is (
The amount is usually 0 to 10% by weight, preferably 0.1 to 5% by weight based on the total of B) and (C). In the present invention (
A) In addition to thermoplastic resins, thermosetting resins such as epoxy resins and alkyd resins can be used in combination.

Further, known additives for thermoplastic resins such as stabilizers, fillers, colorants, surfactants, etc. can be added.

Examples of fillers include ordinary inorganic fillers, fiber components such as glass fiber and carbon fiber, metal powders such as aluminum, iron, copper, and stainless steel, and whiskers.

The amount of filler added is usually 100% by weight or less, preferably 50% by weight or less, based on the total of (A) CB) and (C).

It is also possible to use the usual plasticizers for thermoplastics.
Examples of plasticizers that can be used include dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, butylbenzyl phthalate, dioctyl sebacate, tricresyl phosphate, and polyester plasticizers.

The amount of plasticizer added is usually 5 parts per 100 parts of thermoplastic resin.
It is 0 parts by weight or less, preferably 30 parts by weight or less.

In order to adjust the viscosity of the composition of the present invention when applied to a metal plate, a solvent or the like may be used if necessary.

Preferred solvents include aliphatic saturated hydrocarbons such as cyclohexane, n-hebutane, and mineral spirits;
Aromatic hydrocarbons such as benzene, toluene, xylene,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone,
Examples include esters such as butyl acetate.

The amount of solvent used is generally 100% by weight or less, preferably 70% by weight or less, based on the composition of the present invention.

The method for producing the composition of the present invention is not particularly limited, and for example, it can be obtained by blending (A) into a mixture of (B) and other additives used as necessary, and subjecting the composition to defoaming treatment. .

The resulting composition has a pot life of 2 months or more at 35°C, and a single lot of the composition can be used for a long period of time without waste.

To produce a sandwich-type damping material using the composition of the present invention, the composition of the present invention is coated on a metal plate, and usually
After eliminating fluidity at 0 to 200°C, preferably 80 to 180°C, two metal plates thus obtained are laminated together.
0.5-2 at 80-250℃ under pressure of 00 Kg/c♂
Heat for 0 minutes to bond.

Since the composition of the present invention does not have much fluidity under the above conditions, metal plates can be firmly bonded without the resin protruding from the gaps between the metal plates during pressure bonding.

[Examples] The present invention will be explained below using Examples, but the present invention is not limited thereto. Parts in Examples indicate parts by weight.

Example 1 Vinyl chloride resin (degree of polymerization 800) 60 parts Hydroxyethyl acrylate with an average of 2 moles of caprolactone added per molecule (Daicel Chemical Plaxel FA2) 50 parts t
-Butyl peroxybenzoate 0.4 part Mercaptotin acetate 0.6 part Toluene
10 parts were blended and defoamed under reduced pressure to obtain a composition of the present invention.

The viscosity of this product was 800 centivoids. This composition was applied to a thickness of 30 μm on a steel plate, and the solvent was volatilized in an oven at 120° C., and the vinyl chloride resin was plasticized. The two thus obtained steel plates were laminated together with their resin surfaces and crimped under a pressure of 10 kg/c♂ using a hot press at 200° C. to obtain a vibration damping material of the present invention.

Example 2 50 parts of vinyl chloride resin (degree of polymerization 800)
Droxyethyl acrylate added with an average of 2 moles of caprolactone per molecule (Plaxel FA2 manufactured by Daicel Chemical) 40 parts Prepolymer obtained from 2 moles of polycaprolactone diol with an average molecular weight of 4000 and 3 moles of tolylene diisocyanate and 2 moles 10 parts of urethane acrylate obtained from hydroxyethyl acrylate
A composition and a damping material of the present invention were obtained in the same manner as in Example 1 from 0.4 parts of -butyl peroxybenzoate and 15 parts of xylene.

The viscosity of this composition was 1200 centivoise.

Example 3 Vinyl chloride resin 60 parts Hydroxyethyl methacrylate added with an average of 3 moles of caprolactone per molecule (Daicel Chemical's Plaxel FA3) 40 parts Made from 3 moles of polycaprolactone diol with an average molecular weight of 4000 and 4 moles of tolylene diisocyanate Urethane acrylate obtained from the obtained prepolymer and 2 moles of hydroxyethyl acrylate 100 parts t-butylperoxybenzony 0.2 part di-t-
A composition and a damping material of the present invention were obtained in the same manner as in Example 1 from 0.2 parts of butyl peroxide, 0.6 parts of mercaptotin acetate, and 0.6 parts of mercaptotin acetate.

Comparative Example 1 A comparative composition and vibration damping material were obtained in the same manner as in Example 1, except that the vinyl chloride resin of Example 1 was not used.

Comparative Example 2 Urethane acrylate obtained from a prepolymer obtained from 3 moles of polycaprolactone diol having an average molecular weight of 4000 and 4 moles of tolylene diisocyanate and 2 moles of hydroxyethyl acrylate 100 parts t-
A comparative composition and damping material were obtained in the same manner as in Example 1 from 0.5 parts of butyl peroxybenzoate and 0.5 parts of di-t-butyl peroxide.

Test Example 1 The shear strength and damping rate of the damping materials obtained in Examples 1 to 3 and Comparative Example 1.2 were measured. The measurement results are shown in Table 1.

Table 1 [Effects of the Invention] The composition of the present invention has good adhesion to metals, and when used as a vibration damping material, has a high level of vibration damping performance over a wide temperature range. In addition, it has a very long pot life and is useful in terms of work and storage.

Furthermore, during initial heating, the thermosetting resin component enters the thermoplastic component and loses fluidity, so when two metal plates are crimped together, the resin will not flow out due to the pressure, making the sandwich-type vibration damping material extremely useful. can be easily manufactured.

Due to the above effects, the composition and vibration damping material of the present invention can solve noise problems associated with vibrations of automobiles, home appliances, etc.
It is useful as a vibration damping material composition and a vibration damping material used to maintain the accuracy of precision equipment.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing the structure of the vibration damping material of the present invention. drawing

Claims (1)

[Claims] 1. (A) thermoplastic resin, (B) monofunctional polymerizable monomer,
and, if necessary, (C) a polyfunctional polymerizable monomer and/or
or (D) a resin composition for vibration damping material comprising a polymerization initiator. 2. The composition according to claim 1, wherein (A) is a vinyl chloride resin. 3. The composition according to claim 1 or 2, wherein (B) is caprolactone-modified (meth)acrylate. 4. A vibration damping material having an intermediate layer between a plurality of metal plates, wherein the intermediate layer is made of a cured product of the composition according to any one of claims 1 to 3. 5, (A) thermoplastic resin, (B) monofunctional polymerizable monomer,
and, if necessary, (C) a polyfunctional polymerizable monomer and/or
or (D) a damping material characterized by applying a resin composition comprising a polymerization initiator onto a metal plate, removing fluidity by heat, and then bonding the resultant material together under heat and pressure to obtain a damping material. manufacturing method.