JPH10139973A - Acrylic multilayer polymer particles and composition thereof - Google Patents

Abstract

(57) [Abstract] [Problem] It has excellent vibration damping properties in the general living temperature range,
In addition, the present invention provides a polymer material that provides a resin composition having excellent impact resistance and surface gloss. The present invention has a layer (I) inside and a layer (II) as an outermost layer, and the weight ratio of (I) / (II) is 60/40 to 95/5. Certain multilayer structured polymer particles. The layer (I) was formed by adding acrylic acid ester to 2-99.
It consists of a copolymer of a monomer mixture containing 99% by weight and 0.01 to 10% by weight of a polyfunctional monomer, and the main dispersion of loss tangent (tan δ) of dynamic viscoelasticity shows a peak value. Temperature is 0
℃ to 40 ℃, the peak value is 0.1 or more. Layer (II)
Is a copolymer of a monomer mixture containing 40 to 99% by weight of methacrylic acid ester, and the temperature at which the main dispersion of tan δ shows a peak value is 50 ° C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an acrylic multi-layer polymer particle satisfying specific conditions for the peak value of the main dispersion of the loss tangent (tan δ) of dynamic viscoelasticity and its temperature, and the multilayer structure. The present invention relates to a composition comprising polymer particles and a synthetic resin. The multilayer polymer particles of the present invention have excellent vibration damping performance and weather resistance, are flexible, and have good handleability. Further, the composition of the present invention is not only excellent in surface glossiness, impact resistance and weather resistance but also excellent in vibration damping performance due to the compounding of the multilayer polymer particles.

[0002]

2. Description of the Related Art In recent years, there has been a demand for comfort due to quietness in a living environment. For example, in automobiles, household appliances such as refrigerators, washing machines, and vacuum cleaners; and office equipment such as copiers and printers. There is a strong demand for low vibration and low noise. In addition, in audio equipment, it is required to realize high-quality sound quality by suppressing vibration of a specific frequency. In order to meet these requirements, a vinyl cyanide compound-aromatic vinyl compound copolymer, an olefin resin, and an aromatic vinyl compound polymer block have a vinyl bond amount of 40% or more and a tan δ of 0 ° C. or more. There has been proposed a thermoplastic resin composition containing isoprene having a peak value of the main dispersion of (1) or a block copolymer composed of isoprene and a polymer block of butadiene (JP-A-5-279543). Also, mechanical strength,
In order to improve the balance between rigidity and vibration damping properties, an acrylate-based copolymer or an aromatic vinyl compound-
A resin composition comprising a polymer having a glass transition temperature (hereinafter, abbreviated as “Tg”) selected from conjugated diene compound-based copolymers of 0 ° C. or higher and a thermoplastic resin (JP-A-6-41443)
Publication), a rubber-reinforced methacrylate resin as an essential component, and having a tan δ at 25 ° C. of 0.035.
The above-mentioned thermoplastic resin composition (JP-A-6-20707)
No. 9), methacrylic ester copolymers and Tg
Contains a polymer at −65 ° C. to −20 ° C., and −30 ° C. to +
A thermoplastic resin composition having a tan δ at 40 ° C. of 0.035 or more (JP-A-7-90126) has been proposed.

[0003]

However, in the thermoplastic resin composition described in JP-A-5-279543 described above, although the vibration damping property is improved as compared with the ABS resin, the thermoplastic resin composition is improved. Insufficient properties such as impact properties and surface gloss. On the other hand, JP-A-6-41443, JP-A-6-207079 and JP-A-7-90 described above.
The composition described in Japanese Patent No. 126 is still insufficient in damping properties in a general living temperature range.

An object of the present invention is to provide a polymer material which provides a resin composition which is excellent in vibration damping properties in a general living temperature range, and is also excellent in impact resistance and surface gloss, and a resin composition having these properties Is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies on the above points, the present inventors have found that when specific multi-layered polymer particles are blended with a synthetic resin, the vibration damping properties in a general living temperature range are reduced. It has been found that a resin composition which is excellent and has excellent impact resistance and surface gloss can be obtained. As a result of further studies, the present invention has been completed.

That is, the present invention firstly provides

(1) It has the following layer (I) inside and has the following layer (II) as at least the outermost layer;

(2) The layer (I) is made of acrylic ester 2
９９99.99% by weight, methacrylic acid ester 0 to 97.
A sine wave having a frequency of 10 Hz, comprising a copolymer of a monomer mixture consisting of 99% by weight, 0.01 to 10% by weight of a polyfunctional monomer and 0 to 50% by weight of another copolymerizable monomer. A layer in which the temperature at which the main variance of the loss tangent (tan δ) of dynamic viscoelasticity measured by vibration shows a peak value is 0 ° C to 40 ° C and the peak value is 0.1 or more;

(3) The layer (II) is composed of 40 to 99% by weight of a methacrylate ester and 60 to 1 of other copolymerizable monomers.
The temperature at which the main dispersion of the dynamic viscoelasticity loss tangent (tan δ), which is measured by sine wave excitation at a frequency of 10 Hz, shows a peak value, is 50%.
A layer having a temperature of at least ℃;

(4) The ratio of the total weight of the layer (I) to the total weight of the layer (II) is 60/40 to 95 in (I) / (II).
/ 5;

[0011] The present invention is a polymer particle having a multilayer structure.

Secondly, the present invention is a composition containing the above-mentioned multilayer polymer particles in a proportion of 5% by weight or more and other synthetic resins in a proportion of 95% by weight or less.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The multi-layered polymer particles of the present invention are formed of the layer (I)
And at least one layer (II) in the outermost layer. The number of layers constituting the multilayer polymer particles of the present invention may be two or more, and may be three or four or more. In the case of a two-layer structure, it has a layer (I) (center layer) / layer (II) (outermost layer) structure, and in the case of a three-layer structure, layer (II) (center layer) / layer (I) ( (Intermediate layer) / layer (II) (outermost layer), layer (I) (center layer) / layer (I) (intermediate layer) / layer (II) (outermost layer) or layer (I) (center layer) / layer (II) (Intermediate layer) / Layer (II)
In the case of a four-layer structure, for example, layer (I) (center layer) / layer (II) (intermediate layer) / layer (I) (intermediate layer) / layer (II) (Outermost layer). Among them, layer (I) (center layer) / layer (II) in terms of excellent handleability and flexibility.
(Outermost layer); or layer (II) (center layer) / layer (I) (intermediate layer) / layer (II) (outermost layer) or layer (I) (center layer) / layer (I ) (Intermediate layer) / layer (II) (outermost layer).

The ratio of the total weight of the layer (I) to the total weight of the layer (II) is 60/40 to 95 in (I) / (II).
/ 5. When the ratio of the layer (I) is smaller than this range, the vibration damping performance of the multilayer polymer particles becomes insufficient. Conversely, when the proportion of the layer (I) is larger than this range, it is difficult to form the layer structure in a perfect form, the mechanical strength becomes insufficient, and the melt fluidity extremely decreases.
In addition, the total weight of the layer (I) is the weight of the layer (I) in the multilayer structure polymer particle when there is only one layer, and when the layer (I) is two or more layers, It is the sum of the weights of those layers. Similarly, the total weight of the layer (II) refers to the weight of the layer (II) in the case where only one layer (outermost layer) in the multilayer polymer particle is present. In the above case, it is the sum of the weights of those layers.

The layer (I) in the multilayer polymer particles of the present invention has a main dispersion of loss tangent (tan δ) of 0 ° C. to 40 ° C. when dynamic viscoelasticity is measured by sine wave excitation at a frequency of 10 Hz. It is necessary to show a peak value at a temperature in the range of ° C. and to have the peak value of 0.1 or more. If the temperature at which the peak value is shown is lower than 0 ° C., the temperature is in the normal temperature range (that is, at or near room temperature).
Does not exhibit sufficient damping performance. Conversely, when the temperature at which the peak value is shown is higher than 40 ° C., sufficient vibration damping performance is not exhibited in the normal temperature range, and the molded article obtained from the multilayer polymer particles becomes extremely brittle. In addition, the composition with a synthetic resin also has insufficient impact resistance. If the peak value of the main variance of tan δ is smaller than 0.1, sufficient vibration damping performance cannot be obtained. From the viewpoint of the vibration damping performance of the multilayer polymer particles, the peak temperature is preferably in the range of 10 ° C to 30 ° C, and the peak value is preferably 0.3 or more.

The layer (II) in the multilayer polymer particles of the present invention has a main dispersion of a loss tangent (tan δ) of 50 ° C. or more when dynamic viscoelasticity is measured by sine wave excitation at a frequency of 10 Hz. It is necessary to show a peak value at the temperature. When the temperature is lower than 50 ° C., the resulting multilayer structure polymer particles are difficult to handle because the adhesiveness of the multilayer structure polymer particles becomes remarkable, and further, in the production of the multilayer structure polymer particles, the process passability such as heating, washing, and drying is significantly reduced. This is not preferred.

Specific examples of the acrylate used to form the layer (I) include methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate,
An alkyl acrylate such as dodecyl acrylate or octadecyl acrylate; an ester of acrylic acid such as phenyl acrylate with a phenol; an ester of acrylic acid such as benzyl acrylate with an aromatic alcohol; When the polymer particles have two or more layers (I), they are used alone or as a mixture of two or more in the range of 2 to 99.99% by weight based on the weight of each layer (I)). Can be

Specific examples of the methacrylic acid ester which may be used for forming the layer (I) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and s-butyl. Methacrylate, t-butyl methacrylate, propyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate,
Methacrylic acid alkyl esters such as myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate and octyl dodecyl methacrylate; esters of methacrylic acid such as phenyl methacrylate with phenols; esters of methacrylic acid such as benzyl methacrylate and aromatic alcohols And, if necessary, 97.99% by weight or less based on the weight of the layer (I) (when the multilayer polymer particle has two or more layers (I), each layer (I)). Can be used alone or in combination of two or more.

The polyfunctional monomer used to form the layer (I) is a monomer having two or more carbon-carbon double bonds in the molecule, for example, acrylic acid, methacrylic acid, Unsaturated carboxylic acids such as cinnamic acid and allyl alcohol,
Esters with unsaturated alcohols such as methallyl alcohol or glycols such as ethylene glycol and butanediol; esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and maleic acid with the above unsaturated alcohols; Specifically, allyl acrylate, methallyl acrylate, allyl methacrylate, methallyl methacrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate,
Examples include diallyl isophthalate, divinylbenzene, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth) acrylate. Among these polyfunctional monomers, allyl methacrylate is particularly preferred. The term "di (meth) acrylate" means a general term for "diacrylate" and "dimethacrylate". The polyfunctional monomer is a layer (I) (each layer (I) when the multilayer polymer particle has two or more layers (I)).
Is used alone or in combination of two or more kinds in the range of 0.01 to 10% by weight with respect to the weight of. When the amount of the polyfunctional monomer is less than 0.01% by weight, the layer (I) in the multilayer polymer particles at the time of molding in the composition with the multilayer polymer particles or the synthetic resin thereof has a layer structure. Cannot be maintained, and the mechanical strength of the obtained molded article is insufficient, which is not preferable. On the other hand, if the amount of the polyfunctional monomer is more than 10% by weight, the multilayer structure polymer particles do not show rubber-like elasticity, and the vibration damping performance is reduced. It is not preferable because it causes a decrease.

In order to form the layer (I), other copolymerizable monomers can be used in addition to the acrylate, methacrylate and polyfunctional monomers. The other monomers include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene,
-Propylstyrene, 4-cyclohexylstyrene, 4
-Aromatic vinyl monomers such as dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; butadiene , Isoprene, 2,3-dimethylbutadiene, 2-
Methyl-3-ethylbutadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2-ethyl-
1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 3,4-dimethyl-1,
Conjugated diene-based monomers such as 3-hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, cyclopentadiene, chloroprene, and myrcene, and the like. Layer (I) (when the multilayered polymer particles have two or more layers (I), each alone or in a mixture of two or more at a ratio of 50% by weight or less based on the weight of each layer (I)) Can be used. 50% by weight of the above other monomers
When it exceeds, the weather resistance of the multilayer polymer particles becomes insufficient, which is not preferable.

For the layer (I), the main dispersion of tan δ as described above shows a peak value at a temperature in the range of 0 ° C. to 40 ° C., and the peak value becomes 0.1 or more. May be appropriately selected from the types and combinations of monomers. For example, in order to form layer (I), n-butyl acrylate is used as an acrylate ester, methyl methacrylate is used as a methacrylate ester, When allyl methacrylate is used as the reactive monomer, n-butyl acrylate is 52.25 to 74.
Within the range of 99% by weight, and methyl methacrylate
When good results are obtained by selecting the use ratio of each monomer in such a ratio that the content is within the range of 2.75 to 25% by weight and the amount of allyl methacrylate is within the range of 0.01 to 5% by weight. There are many.

The layer (II) of the present invention is obtained by polymerizing 40 to 99% by weight of a methacrylic acid ester and 60 to 1% by weight of another monomer copolymerizable therewith. If the methacrylate is less than 40% by weight, the weather resistance is insufficient,
If it is more than 99% by weight, the heat stability is insufficient, which is not preferable.

Specific examples of the methacrylic acid ester include:
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate and isobornyl methacrylate, and the like. Is methyl methacrylate.

The other copolymerizable monomers include, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-
Alkyl acrylates such as butyl acrylate;
Styrene, α-methylstyrene, 3-methylstyrene,
Aromatic vinyl monomers such as halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide; N-cyclohexylmaleimide, N-
Maleimide monomers such as phenylmaleimide, N- (p-bromophenyl) maleimide, and N- (p-chlorophenyl) maleimide; and polyfunctional monomers as exemplified above. Among these, alkyl acrylates such as methyl acrylate, ethyl acrylate and n-butyl acrylate are preferred.

In the multilayer polymer particles of the present invention, the outermost layer and / or the layer inscribed in the outermost layer may be composed of a copolymer in which a monomer having a functional group is copolymerized. When a composition with a resin is formed into a molded product, it is preferable from the viewpoint of excellent mechanical strength. Examples of the monomer having a functional group include a hydroxyl group-containing monomer such as 2-hydroxy (meth) acrylate and 3-hydroxypropyl (meth) acrylate; and an epoxy group-containing monomer such as glycidyl (meth) acrylate and p-glycidylstyrene. Monomer; carboxyl group-containing monomer such as (meth) acrylic acid and maleic anhydride;
-Amino group-containing monomer such as-(dimethylamino) ethyl (meth) acrylate; monomer having a group such as t-butyl methacrylatecarbamate that has a protective group which is removed under heating conditions to change into a functional group Are preferred.

The polymerization method for producing the multi-layered polymer particles of the present invention is not particularly limited. For example, an emulsion polymerization method may be used according to a known polymerization method for producing ordinary multi-layered polymer particles. The multilayer polymer particles of the present invention can be produced by a suspension polymerization method, a bulk polymerization method, a solution polymerization method or a combination thereof.

For example, in the emulsion polymerization method, desired multilayer structure particles can be obtained by sequentially performing polymerization for forming each layer according to a known means. The temperature of the emulsion polymerization is not particularly limited.
A temperature in the range of １００100 ° C. is common. Here, rosinates such as potassium rosinate; alkali metal salts of fatty acids such as sodium oleate, sodium laurate and sodium stearate; sulfate salts of aliphatic alcohols such as sodium lauryl sulfate; dodecylbenzene sulfone; An alkylarylsulfonic acid such as an acid can be used, and these can be used alone or in combination of two or more. In emulsion polymerization, a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like can be used alone as a radical polymerization initiator. Further, as the radical polymerization initiator, a redox initiator obtained by combining an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, or paramenthane hydroperoxide with a reducing agent can be used. Representative examples of the redox initiator include a dextrose formulation comprising organic hydroperoxides, ferrous sulfate, sodium pyrophosphate and dextrose; organic hydroperoxides, ferrous sulfate, disodium ethylenediaminetetraacetate and formaldehyde. And a sulfoxylate formulation comprising sodium sulfoxylate. In the emulsion polymerization, if necessary, a molecular weight regulator can be used according to known means. Representative examples of the molecular weight regulator include mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and mercaptoethanol; terpene mixtures composed of terpinolene, dipentene, t-terpinene and a small amount of other cyclic terpenes. A halogenated hydrocarbon such as chloroform and carbon tetrachloride.

After the emulsion polymerization, the obtained multi-layered polymer particles can be separated and obtained from the polymerization reaction system according to a known method, for example, an acid precipitation method, a salt precipitation method, a spray drying method, a freeze coagulation method. Etc. can be adopted.

As described above, the multilayer polymer particles of the present invention can be obtained in various forms such as powders and pellets. When the multi-layered polymer particles of the present invention are in an aggregated form such as pellets, they may be fused to each other in the outermost layer, but under heating conditions because the outermost layer has thermoplasticity. It can be easily separated by applying a shearing force.

The average particle size of the multilayer polymer particles of the present invention is not particularly limited, but is preferably 50 to 15
It is preferably in the range of 00 nm. When the thickness is 50 nm or more, the melt fluidity of the multilayer polymer particles is improved, and the moldability is improved. Further, when the thickness is 1500 nm or less, the surface gloss in the case where the composition of the multilayer structure polymer particles and the synthetic resin is used as a molded article is particularly improved.

Since the outermost layer of the multilayer polymer particles of the present invention has thermoplasticity, it is easy to prepare a composition of the multilayer polymer particles and another synthetic resin.

In the composition comprising the polymer particles having a multilayer structure of the present invention and another synthetic resin, the content of the polymer particles having a multilayer structure is not less than 5% by weight in order to exhibit excellent vibration damping performance. The content of the synthetic resin is preferably 95% by weight or less. However, if the content of the multilayer polymer particles is too high, the physical properties of the synthetic resin tend to be lost. Therefore, in order to achieve both the vibration damping performance and the characteristics of the synthetic resin, the multilayer polymer particles / More preferably, the weight ratio of the synthetic resin is in the range of 25/75 to 75/25.

The other synthetic resin is not particularly limited, and any of a thermoplastic resin and a thermosetting resin can be used. Specific examples of the thermoplastic resin include polystyrene, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, high impact polystyrene, ABS, AES, AAS, ACS,
Styrene resins such as MBS; Acrylic resins such as polymethyl methacrylate, methyl methacrylate-styrene copolymer, and other acrylic core-shell polymers (multilayer structure polymers); Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Nylon 6, polyamides such as nylon 66 and polyamide elastomer; polyethylene, polypropylene, polybutene
1, polyolefin resins such as poly-4-methylpentene-1 and polynorbornene; ethylene ionomer; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl alcohol copolymer; ethylene-vinyl acetate copolymer Coalescent; polyacetal; polyvinylidene fluoride; polyurethane, modified polyphenylene ether; polyphenylene sulfide; silicone rubber-modified resin.
Further, specific examples of the thermosetting resin include an epoxy resin,
Unsaturated polyester, phenolic resin, urea resin, melamine resin and the like can be mentioned.

The composition comprising the polymer particles having a multilayer structure and the synthetic resin of the present invention may contain various known additives (for example, rubbers, lubricants, antioxidants, plasticizers) within a range not to impair the purpose of the present invention. Agents, light stabilizers, coloring agents, antistatic agents, flame retardants, etc.), fillers (eg, fiber reinforcing agents such as glass fibers, inorganic fillers, etc.) and the like. Examples of the rubber include styrene-based TPE (thermoplastic elastomer) such as SEPS, SEBS, and SIS; IR, EP
R, EPDM and other olefin rubbers; acrylic or silicone rubbers and the like can be used. Examples of the lubricant include stearic acid, behenic acid, stearamic acid, methylene bisstearamide, hydroxystearic acid triglyceride, and paraffin. Wax, ketone wax, octyl alcohol, hardened oil and the like can be used. As the antioxidant, for example, 2,6-di-
t-butyl-4-methylphenol, stearyl β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, triethylene glycol-bis-3-
Phenolic compounds such as (3-t-butyl-4-hydroxy-5-methylphenyl) propionate; N, N-
Amine compounds such as di-2-naphthyl-p-phenylenediamine and the like can be used. As the plasticizer, for example, di-2-ethylhexyl phthalate, polyethylene glycol and the like can be used. As the light stabilizer, for example, pt-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2-hydroxy-4-n-octyloxyphenyl) benzotriazole, or the like is used. Can be. As the coloring agent, for example, titanium oxide, carbon black, other inorganic or organic pigments, and the like can be used. As the antistatic agent, for example, stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate and the like are used. Examples of the flame retardant include organic halogen-based flame retardants such as tetrabromobisphenol A, decabromodiphenyl oxide, and brominated polycarbonate; and non-halogen-based flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, and tricresyl phosphate. Can be used.

The composition containing the polymer particles having a multilayer structure and the synthetic resin of the present invention is characterized in that when the synthetic resin is a thermoplastic resin,
For example, it can be produced by mixing the multilayer structure polymer particles, the synthetic resin and other components used as desired under melt-kneading conditions. When the synthetic resin is a thermosetting resin, it can be produced, for example, by mixing the polymer particles having a multilayer structure with the synthetic resin (thermosetting resin). Mixing the structural polymer particles with the thermosetting resin in the form of a solution with a solvent,
Next, a method of evaporating the solvent may be applied.

The multi-layered polymer particles of the present invention can be thermally molded because the outermost layer has thermoplasticity, and can be formed by extrusion, injection molding, hollow molding, calendar molding, compression molding, foam molding, vacuum molding, or the like. Sheet, by molding method such as molding
It can be formed into a molded article of any shape such as a film, a tube, a hollow article (a bottle, etc.). Examples of the use of the molded article from the multilayer polymer particles alone include desk mats,
Soft members for automobile interiors and the like can be mentioned. Further, the composition containing the multilayer structure polymer particles of the present invention and a synthetic resin is a thermoplastic resin or a thermosetting resin, respectively, depending on whether the synthetic resin used is a thermoplastic resin or a thermosetting resin. The molding method employed for the curable resin can be employed. For example, when the synthetic resin is a thermoplastic resin, extrusion molding, injection molding, hollow molding, calendar molding,
Molding methods such as compression molding, foam molding, and vacuum molding can be adopted.If the synthetic resin is a thermosetting resin, molding methods such as cast molding, injection molding, and compression molding are employed. be able to. By these molding methods, it can be molded into a molded article of an arbitrary shape such as a sheet, a film, a tube, a hollow article (a bottle or the like), a box-shaped article, or the like. Examples of uses of molded articles from the composition include chassis for refrigerators, washing machines, vacuum cleaners, etc .; housings for copiers, printers, etc .; hard members for automobile interiors, speaker parts, and the like.

[0038]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, each measured value in an Example followed the following evaluation method.

The peak value of the main variance of the loss tangent (tan δ) and the temperature (Tα) at that time are determined by the viscoelasticity analyzer “D
VE-V4 "(manufactured by Rheology Co., Ltd.) was obtained by applying a sinusoidal vibration with a frequency of 10 Hz and an amplitude of 3 μm in the tensile direction to a test piece having a length of 25 mm × a width of 5 mm × a thickness of 1 mm by a forced vibration non-resonance method. It was determined by measuring the dynamic viscoelastic spectrum.

The average particle size of the polymer particles having a multilayer structure was measured by a dynamic light scattering method using a laser particle size analyzer PAR-III (manufactured by Otsuka Electronics Co., Ltd.) and analyzed by a cumulant method.

The tensile strength at break and the stress at 100% elongation (100% modulus) were in accordance with JIS K6301.

The flexural yield strength and flexural modulus were determined by ASTM.
D 790.

The Izod impact strength was measured according to ASTM D 2
56 (notched, 23 ° C.).

The light-coloring resistance was determined by measuring the lightness index L and the chromaticness indices a and b in the color difference formula of Hunter before and after the treatment with Tosquer (manufactured by Toshiba Kikai Co., Ltd.) for a predetermined time. And SM-4), based on tristimulus values specified in JIS Z 8722, and using these indices, a color difference ΔE was obtained from a hunter's color difference formula, and the color difference ΔE was evaluated. It can be evaluated that the smaller the color difference ΔE is, the better the light-coloring resistance is.

Regarding the heat-resistant coloring property, indices L, a and b were measured before and after the treatment with a hot air dryer at 160 ° C. for a predetermined time in the same manner as in the evaluation of the light-coloring resistance, and these indices were measured. To obtain a color difference ΔE, and evaluated by the color difference ΔE. It can be evaluated that the smaller the color difference ΔE, the better the heat resistance coloring property.

The vibration damping performance was evaluated by the value of tan δ or the loss factor (η) at 20 ° C. by the above measurement. The loss coefficient (η) is 100 mm long × 10 mm wide × 3 m thick
According to a resonance method, a test piece of m was vibrated by a vibrator and the degree of resonance of the test piece was measured. The measurement frequency was 500 Hz and the measurement temperature was 23 ° C.

The surface gloss was evaluated on the basis of the average value of the gloss values of the gate portion and the end portion of the dumbbell test piece according to ASTM D 638. Average value is 85
% Or more was evaluated as good (○), and less than 85% was evaluated as poor (x). The incident angle of the light source was 60 degrees.

Example 1 In a nitrogen atmosphere, 600 parts by weight of distilled water and 2.5 parts by weight of potassium dodecylbenzenesulfonate as an emulsifier were added to a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel. The mixture was heated to 70 ° C. and uniformly dissolved. Then, at the same temperature, 100 parts by weight of n-butyl acrylate, 80 parts by weight of methyl methacrylate and 1.5 parts by weight of allyl methacrylate were added, and
After stirring for 1 minute, 0.15 parts by weight of potassium peroxodisulfate was added to initiate polymerization. After 4 hours, gas chromatography confirmed that all the monomers had been consumed. Next, after adding 0.3 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 40 parts by weight of methyl methacrylate and 10 parts by weight of ethyl acrylate were added dropwise from a dropping funnel over 2 hours. After dropping, 70
At 30 ° C., the reaction was further continued for 30 minutes, and upon confirming that the monomer was consumed, the polymerization was terminated. The average particle size of the multilayer polymer particles in the obtained latex was 250 nm. After cooling this to −20 ° C. for 24 hours to coagulate,
The aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayered polymer particle [A-1] in the form of a coagulated powder. The resulting powdery A-
Using No. 1, a sheet was produced by a press molding machine, and various measurements were performed. Tables 1 and 2 show the obtained measurement results and evaluation results.
Shown in

Example 2 In a nitrogen atmosphere, 600 parts by weight of distilled water and sodium stearate as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel.
5 parts by weight were added, and the mixture was heated to 70 ° C. and uniformly dissolved.
Then, at the same temperature, 20 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate and 0.03 parts by weight of allyl methacrylate were added, and after stirring for 60 minutes, 0.04 parts by weight of potassium peroxodisulfate was added to carry out polymerization. Started. Two hours later, gas chromatography confirmed that all the monomers had been consumed. After 0.3 parts by weight of potassium peroxodisulfate was added to the obtained copolymer latex, 150 parts by weight of methyl acrylate and 0.2 part by weight of allyl methacrylate were added dropwise from a dropping funnel over 2 hours. After completion of the dropwise addition, the reaction was further continued at 70 ° C. for 1 hour, and it was confirmed that the monomer was consumed. Next, after adding 0.03 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 20 parts by weight of methyl methacrylate and 5 parts by weight of ethyl acrylate were added to a dropping funnel at a rate of 1 part.
It was dropped over time. After the completion of the dropwise addition, at 70 ° C.,
The reaction was continued for 0 minutes, and upon confirming that the monomer was consumed, the polymerization was terminated. The average particle size of the multilayer polymer particles in the obtained latex was 230 nm. This is -2
After cooling to 0 ° C. for 24 hours for aggregation, the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, at 50 ° C., 2
It was dried under reduced pressure for days to obtain aggregated powdery multilayer polymer particles [A-2]. A sheet was produced using the obtained powdered A-2 by a press molding machine, and various measurements were performed. Tables 1 and 2 show the obtained measurement results and evaluation results.

Example 3 Under a nitrogen atmosphere, 600 parts by weight of distilled water and sodium stearate as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel.
5 parts by weight were added, and the mixture was heated to 70 ° C. and uniformly dissolved.
Then, at the same temperature, 36 parts by weight of methyl methacrylate, 144 parts by weight of ethyl acrylate and 0.04 parts by weight of allyl methacrylate were added, and the mixture was stirred for 60 minutes, and then 0.04 parts by weight of potassium peroxodisulfate was added to polymerize. Started. Two hours later, gas chromatography confirmed that all the monomers had been consumed. Subsequently, the obtained copolymer latex was added with potassium peroxodisulfate 0.0%.
After adding 3 parts by weight, 18 parts by weight of methyl methacrylate and 2 parts by weight of n-butyl acrylate were dropped from the dropping funnel over 1 hour. After the completion of the dropping, at 70 ° C., another 30
The reaction was continued for another minute, and the polymerization was terminated after confirming that the monomer was consumed. The average particle size of the multilayer polymer particles in the obtained latex was 205 nm. This is -20
After cooling to 24 ° C. for 24 hours for aggregation, the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, at 50 ° C., 2
It was dried under reduced pressure for days to obtain aggregated powdery multilayer polymer particles [A-3]. A sheet was prepared using the obtained powdered A-3 with a press molding machine, and various measurements were performed. Tables 1 and 2 show the obtained measurement results and evaluation results.

Example 4 Distilled water 20 was placed in an autoclave.
0 parts by weight, potassium rosinate 2 parts by weight, Rongalit (sodium formaldehyde sulfoxylate) 0.
267 parts by weight, 0.1 parts by weight of disodium ethylenediaminetetraacetate, 0.008 parts by weight of ferrous sulfate heptahydrate, 0.04 parts by weight of potassium hydroxide, and 1.2 parts by weight of potassium carbonate were charged and stirred. The temperature was raised to 50 ° C. while purging with nitrogen. After 30 minutes, 24 parts by weight of butadiene, 52 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate and 0.5 part by weight of divinylbenzene were added, and stirring was continued for 30 minutes while maintaining this temperature. Then, at the same temperature, 0.1 part by weight of cumene hydroperoxide was added to initiate polymerization. Four hours later, gas chromatography confirmed that all the monomers had been consumed. Next, the obtained polymer latex was heated to 70 ° C., 0.2 parts by weight of potassium peroxodisulfate was added, and methyl methacrylate 1 was added.
A mixture of 8 parts by weight, 2 parts by weight of methyl acrylate and 0.2 part by weight of tert-dodecyl mercaptan was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued at 70 ° C. for another 30 minutes, and the polymerization was terminated after confirming that each monomer was consumed. The average particle size of the multilayer polymer particles in the obtained latex was 150 nm. Bring this to -20 ° C
After cooling for 4 hours for coagulation, the coagulated material is taken out and
Washed three times with hot water at ℃. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained multilayered polymer particle [A-4] in the form of a coagulated powder.
I got A sheet was prepared using the obtained powdered A-4 by a press molding machine, and various measurements were performed. Tables 1 and 2 show the obtained measurement results and evaluation results.

Example 5 Under a nitrogen atmosphere, 600 parts by weight of distilled water and 1.5% of sodium stearate as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel.
A part by weight was added, and the mixture was heated to 70 ° C. and uniformly dissolved. Then, at the same temperature, 153.6 parts by weight of ethyl acrylate, 38.4 parts by weight of methyl methacrylate and 0.8 parts by weight of allyl methacrylate were added, and the mixture was stirred for 30 minutes.
0.15 parts by weight of potassium peroxodisulfate was added to initiate polymerization. After 4 hours, gas chromatography confirmed that all the monomers had been consumed. Next, potassium peroxodisulfate was added to the obtained polymer latex at a concentration of 0.1%.
After adding 3 parts by weight, a mixture of 40 parts by weight of methyl methacrylate and 8 parts by weight of 2-hydroxyethyl methacrylate was dropped from the dropping funnel over 2 hours. After dropping,
The reaction was continued at 70 ° C. for another 30 minutes, and the polymerization was terminated after confirming that each monomer was consumed. The average particle diameter of the multilayer polymer particles in the obtained latex is 280 nm.
Met. This was cooled to −20 ° C. for 24 hours to aggregate, and then the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayered polymer particle [A-5] of an agglomerated powder form. A sheet was prepared with a press molding machine using the obtained powdery A-5,
Various measurements were made. Tables 1 and 2 show the obtained measurement results and evaluation results.

Example 6 Under a nitrogen atmosphere, 600 parts by weight of distilled water and sodium stearate as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel.
5 parts by weight were added, and the mixture was heated to 70 ° C. and uniformly dissolved.
Then, at the same temperature, 50 parts by weight of methyl methacrylate, 150 parts by weight of ethyl acrylate and 0.04 parts by weight of allyl methacrylate were added, and after stirring for 60 minutes, 0.04 parts by weight of potassium peroxodisulfate was added to carry out polymerization. Started. Two hours later, gas chromatography confirmed that all the monomers had been consumed. Then, the obtained copolymer latex was added with potassium peroxodisulfate 0.3%.
After adding 2.5 parts by weight of methyl methacrylate,
20 parts by weight of ethyl acrylate, allyl methacrylate 0.
01 parts by weight and 2.5 parts by weight of glycidyl methacrylate were dropped from the dropping funnel over 1 hour. After dropping, 7
The reaction was continued at 0 ° C. for another 1 hour, and it was confirmed that the monomer was consumed. Further, after adding 0.03 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 20 parts by weight of methyl methacrylate and n-acrylic acid were added.
5 parts by weight of butyl was dropped from the dropping funnel over 2 hours. After completion of the dropwise addition, the reaction was continued at 70 ° C. for another 30 minutes, and the polymerization was terminated after confirming that the monomer was consumed. The average particle size of the multilayer polymer particles in the obtained latex was 220 nm. This was cooled to −20 ° C. for 24 hours to aggregate, and then the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayered polymer particle [A-6] in the form of a coagulated powder. A sheet was prepared from the obtained powdered A-6 using a press molding machine, and various measurements were made. Tables 1 and 2 show the obtained measurement results and evaluation results.

Comparative Example 1 In a nitrogen atmosphere, 600 parts by weight of distilled water and 2.5 parts by weight of potassium dodecylbenzenesulfonate as an emulsifier were added to a polymerization vessel equipped with a stirring blade, a cooling pipe, and a dropping funnel. The mixture was heated to 70 ° C. and uniformly dissolved. Then, at the same temperature, acrylic acid n-
After adding 180 parts by weight of butyl and 0.10 parts by weight of allyl methacrylate and stirring for 60 minutes, 0.15 parts by weight of potassium peroxodisulfate was added to initiate polymerization. After 4 hours, gas chromatography confirmed that all the monomers had been consumed. Next, after adding 0.3 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 40 parts by weight of methyl methacrylate and 10 parts by weight of ethyl acrylate were added dropwise from a dropping funnel over 2 hours.
After completion of the dropwise addition, the reaction was continued at 70 ° C. for another 30 minutes, and the polymerization was terminated after confirming that the monomer was consumed. The average particle size of the multilayer polymer particles in the obtained latex was 220 nm. This was cooled to −20 ° C. for 24 hours to be aggregated, and then the aggregate was taken out.
Washed twice. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayered polymer particle [B-1] in the form of an agglomerated powder. A sheet was prepared from the obtained powdered B-1 using a press molding machine, and various measurements were performed. Tables 1 and 2 show the obtained measurement results and evaluation results.

Comparative Example 2 Polystyrene in the form of pellets
Polyisoprene (vinyl group content: about 80%)-polystyrene triblock copolymer (total weight ratio of polystyrene block / polyisoprene block: 20/80; peak value of main dispersion of tan δ in polyisoprene block: 0) .9; the temperature at which the peak value is exhibited: 25 ° C .; the temperature at which the main dispersion of tan δ in the polystyrene block exhibits the peak value: 105 ° C.) [B-2], a sheet is produced by a press molding machine, Various measurements were made. Table 2 shows the obtained measurement results and evaluation results.

[0056]

[Table 1]

In Table 1, the multi-layered polymer particles (B-1) of Comparative Example 1 had n-acrylic acid content.
The inner layer formed by polymerization of butyl and allyl methacrylate is referred to as “layer (I)”, and the outermost layer formed by polymerization of methyl methacrylate and ethyl acrylate is referred to as “layer (I)”.
I) ".

[0058]

[Table 2]

As is evident from the results shown in Tables 1 and 2, the multilayer polymer particles according to the present invention obtained in Examples 1 to 6 have a loss tangent (tan δ) in the vibration damping behavior at 20 ° C. Since the value is large (0.35 or more), the vibration control performance is extremely excellent, and the hardness (JIS-A) is low (95
Therefore, the color difference (ΔE) between the blank (initial) and after 10 hours is small in the light-coloring resistance evaluation test and 24 hours after the blank (initial) in the heat-resistant coloring evaluation test. Color difference (Δ
Since E) is small, it can be seen that the weather resistance is excellent.
On the other hand, the multilayer polymer particles obtained in Comparative Example 1 are shown in Table 1.
As is clear from FIG. 5, the loss tangent (tan) in the layer (I) is
The main dispersion of δ) is different from the multilayer polymer particles of the present invention in that the temperature at which the peak value of the main dispersion is outside the range of 0 ° C to 40 ° C is different from that of the multilayer polymer particles of the present invention. Of the loss tangent (tan δ) in the vibration damping behavior of
9) It turns out that the vibration damping performance is insufficient. Further, the triblock copolymer of Comparative Example 2, which is different from the multilayer polymer particles of the present invention, is excellent in vibration damping performance, as is clear from Table 2, but is evaluated for light-coloring resistance evaluation test and heat-resistant coloring resistance evaluation. The large color difference (ΔE) in the test indicates that the weather resistance is insufficient.

Example 7 A twin-screw extruder comprising 20 parts by weight of the multi-layered polymer particles (A-1) obtained in Example 1 and 80 parts by weight of an ABS resin (Psycolac T, manufactured by Ube Psycon Corp.) By kneading at 220 ° C. and pelletizing to obtain a resin composition. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

Example 8 30 parts by weight of the multilayer polymer particles (A-3) obtained in Example 3 and 70 parts by weight of an AES resin (UCL AXS SE40, manufactured by Ube Sicon) were twin-screw extruded. By kneading at 220 ° C. and pelletizing to obtain a resin composition. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

(Example 9) 30 parts by weight of the multilayer polymer particles (A-4) obtained in Example 4 and 70 parts by weight of polycarbonate (Teflon A2200 manufactured by Idemitsu Petrochemical Co., Ltd.) were mixed with a twin screw extruder. The resin composition was obtained by kneading at 250 ° C. and pelletizing. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

Example 10 40 parts by weight of the multilayer polymer particles (A-5) obtained in Example 5 and 60 of ethylene-polyvinyl alcohol copolymer (EVOH) (Eval EP-E105, manufactured by Kuraray Co., Ltd.) The resin composition was obtained by kneading the mixture with a weight part at 220 ° C. with a twin-screw extruder and pelletizing. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

Comparative Example 3 Methyl methacrylate-methyl acrylate copolymer (B-3) 20 having a single peak of tan δ and a peak temperature of 105 ° C.
A resin composition was obtained by kneading 80 parts by weight of an ABS resin (Psycolac T, manufactured by Ube Sycon Co., Ltd.) at 220 ° C. with a twin screw extruder and pelletizing.
Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

Comparative Example 4 30 parts by weight of the triblock copolymer (B-2) of Comparative Example 2 and 70 parts by weight of an AES resin (UCL AXS SE40, manufactured by Ube Psycon Co., Ltd.) were heated at 220 ° C. using a twin screw extruder. By kneading and pelletizing to obtain a resin composition. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

Comparative Example 5 30 parts by weight of the multilayer polymer particles (B-1) obtained in Comparative Example 1 and 70 parts by weight of polycarbonate (Teflon A2200, manufactured by Idemitsu Petrochemical Co., Ltd.) were subjected to a twin-screw extruder. The resin composition was obtained by kneading at 250 ° C. and pelletizing. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

(Comparative Example 6) 40 parts by weight of an ethyl acrylate-styrene copolymer (B-4) having a single tan δ peak and a peak temperature of 20 ° C, and ethylene-polyvinyl alcohol Copolymer (Kuraray Co., Ltd.)
Eval EP-E105) by kneading at 60 ° C. with a twin screw extruder at 220 ° C. and pelletizing,
A resin composition was obtained. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 3 shows the results of the measurement and evaluation.

[0068]

[Table 3]

In Table 3, "NB" in the column of "Izod impact strength" means "do not break".

As is evident from the results shown in Table 3, the compositions of the multilayer structure polymer particles and the synthetic resin according to the present invention in Examples 7 to 10 show the loss coefficient (η) in the vibration damping behavior at 23 ° C. Is large (0.075 or more), the vibration damping performance is excellent, and the Izod impact strength is large (20 kg · cm / cm or more), the impact resistance is excellent, and the gloss evaluation is “〇”. This shows that the surface gloss is excellent. On the other hand, Comparative Examples 3 to 4 using a polymer different from the multilayer structure polymer particles according to the present invention.
In the composition No. 6, the damping performance was insufficient because the value of the loss coefficient (η) in the vibration damping behavior at 23 ° C. was small (Comparative Examples 3 and 5), or because the Izod impact strength was low, the composition was resistant. Insufficient impact properties (Comparative Examples 3, 4 and 6)
Or, since the gloss evaluation is "x", it can be seen that the surface gloss is insufficient (Comparative Examples 4 and 6).

Example 11 20 parts by weight of the multilayer polymer particles (A-2) obtained in Example 2 and polybutylene terephthalate (PBT) (Hauser KL27 manufactured by Kuraray Co., Ltd.)
3FH) was kneaded with a twin screw extruder at 240 ° C. and pelletized to obtain a resin composition. Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 4 shows the results of the measurement and evaluation.

(Example 12) 15 parts by weight of the multilayer polymer particles (A-6) obtained in Example 6 and polybutylene terephthalate (PBT) (Hauser KL26 manufactured by Kuraray Co., Ltd.)
3F) 85 parts by weight were kneaded with a twin-screw extruder at 240 ° C. and pelletized to obtain a resin composition.
Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 4 shows the results of the measurement and evaluation.

Comparative Example 7 20 parts by weight of the multilayer polymer particles (B-1) obtained in Comparative Example 1 and polybutylene terephthalate (PBT) (Hauser KL273 manufactured by Kuraray Co., Ltd.)
FH) at 80 ° C. with a twin-screw extruder at 240 ° C. and pelletization to obtain a resin composition.
Using the obtained resin composition, test pieces were prepared by an injection molding machine, and various measurements and evaluations were performed. Table 4 shows the results of the measurement and evaluation.

Comparative Example 8 15 parts by weight of the triblock copolymer (B-2) of Comparative Example 2 and polybutylene terephthalate (PBT) (Hauser KL263F, manufactured by Kuraray Co., Ltd.) 8
5 parts by weight were kneaded at 240 ° C. by a twin-screw extruder and pelletized to obtain a resin composition. Using the obtained resin composition to prepare a test piece by an injection molding machine,
Various measurements and evaluations were performed. Table 4 shows the results of the measurement and evaluation.

[0075]

[Table 4]

As is evident from the results shown in Table 4, the compositions of the multilayered polymer particles and the synthetic resin according to the present invention in Examples 11 and 12 showed a loss coefficient (η) in the vibration damping behavior at 23 ° C. Is large (0.050 or more)
From this, it can be seen that the vibration damping performance is excellent, and the color difference (ΔE) in each of the light coloring resistance evaluation test and the heat coloring resistance evaluation test is small, and thus the weather resistance is excellent. On the other hand, in the composition of Comparative Example 7 using the multilayer structure polymer particles different from the multilayer structure polymer particles according to the present invention, the value of the loss coefficient (η) in the vibration damping behavior at 23 ° C. is small. It turns out that the damping performance is insufficient. In addition, the composition of Comparative Example 8 using a triblock copolymer different from the multilayer polymer particles according to the present invention has poor weather resistance due to a large color difference (ΔE) in a heat resistance coloring evaluation test. It turns out to be enough.

[0077]

As described above, according to the present invention, a low-hardness multilayer polymer particle having excellent vibration damping performance and excellent weather resistance is provided. In the composition of the multilayer structure polymer particles and the synthetic resin, good vibration damping performance is exhibited in a general living temperature range due to the compounding of the multilayer structure polymer particles. The composition is also excellent in impact resistance, surface gloss and weather resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yukijun Komiya 41 Miyukigaoka, Tsukuba, Ibaraki Pref.

Claims (3)

[Claims] (1) The layer (I) has the following layer (I) inside and the following layer (II) as at least the outermost layer; ~ 99.99
% By weight, methacrylic acid ester 0 to 99.99% by weight,
It consists of a copolymer of a monomer mixture consisting of 0.01 to 10% by weight of a polyfunctional monomer and 0 to 50% by weight of another copolymerizable monomer, and is measured by sine wave vibration at a frequency of 10 Hz. (3) layer in which the temperature at which the main variance of the loss tangent (tan δ) of the dynamic viscoelasticity to be obtained shows a peak value is 0 ° C to 40 ° C and the peak value is 0.1 or more; (II) consists of a copolymer of a monomer mixture consisting of 40 to 99% by weight of a methacrylic acid ester and 60 to 1% by weight of another copolymerizable monomer, and is measured by sine wave vibration at a frequency of 10 Hz. Loss tangent (tan
δ) is a layer in which the temperature at which the main dispersion of the peak shows a peak value is 50 ° C. or higher; (4) The ratio of the total weight of the layer (I) to the total weight of the layer (II) is:
(I) / (II) is 60/40 to 95/5;
Multilayer polymer particles characterized by the above-mentioned. 2. The multilayered polymer particles according to claim 1, wherein the outermost layer and / or the layer inscribed in the outermost layer comprises a copolymer obtained by copolymerizing a monomer having a functional group. 3. A composition containing the multilayer structure polymer particles according to claim 1 or 2 in a proportion of 5% by weight or more and other synthetic resins in a proportion of 95% by weight or less.