JP2001122932A - Polymer particle of multilayered structure and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain new polymer particles of a multilayered structure capable of providing a molded product having excellent elastic recovery properties, moderate flexibility and good mechanical properties in a well-balanced state. SOLUTION: (1) The polymer particles have (I) a rubber component layer in the innermost part, (II) a rubber component layer on the adjacent part thereof and (III) a thermoplastic resin component layer in the outermost part. (2) The layers (I) and (II) are respectively formed by the copolymerization of a monomer mixture (i) and a monomer mixture (ii) comprising 50-95 wt.% of an acrylic ester, 49.99-0 wt.% of other monofunctional monomers and 0.01-10 wt.% of a polyfunctional monomer. (3) The content (wt.%) of the acrylic ester in the monomer mixture (i) is lower than that (wt.%) of the acrylic ester in the monomer mixture (ii). (4) The layer (III) is formed by the copolymerization of (iii) a monomer mixture comprising 40-99 wt.% of a methacrylic ester and 60-1 wt.% of other monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymer particle having a multilayer structure, and more particularly to a use of the polymer particle having a multilayer structure. More specifically, the present invention relates to specific multi-layer polymer particles containing at least two rubber component layers and at least one thermoplastic resin layer, which have excellent elastic recovery (low permanent set properties), moderate Multilayer polymer particles capable of exhibiting a unique performance of providing excellent flexibility and good other mechanical properties in a well-balanced manner, and a molding material and molded article comprising the multilayer structure polymer particles About. The present invention further relates to a resin composition comprising the multilayer polymer particles and a synthetic resin, a molding material and a molded article comprising the resin composition.

[0002]

2. Description of the Related Art Multilayer polymer particles are also referred to as core-shell type polymers and contain a layer made of a rubber component inside and a layer made of a thermoplastic resin component outside. It is used for modifying thermoplastic resins such as polyvinyl chloride, polyester, and acrylic resin. Among them, it is known to be useful as a modifier for imparting toughness. In the multilayer polymer particles, the number average molecular weight of the thermoplastic resin component constituting the outermost layer of the multilayer polymer particles is usually 3 for the purpose of improving the melt kneading property with other thermoplastic resins.
In the polymerization reaction step for forming the outermost layer, a molecular weight controlling agent such as an alkyl mercaptan is not used at all or is used in order to control the molecular weight. Even in this case, the amount used is generally limited to a small ratio of 0.3% by weight or less based on the monomer.

[0003]

However, a molded article composed of a multilayer polymer particle or a resin composition of the same and a synthetic resin has elastic recovery (that is, low permanent set characteristics), flexibility and other mechanical properties. Looking at the physical properties,
In many cases, either performance is lacking and improvements are desired.

An object of the present invention is to provide a molded article of the resin itself or a resin composition of the resin itself and a synthetic resin, and have excellent elastic recovery (low permanent set) and moderate flexibility (not too hard and soft). And to provide a molded article having a good balance between good mechanical properties and other good mechanical properties. Another object of the present invention is to provide a molding application of the novel multilayer polymer particles. Still another object of the present invention is a resin composition using the novel multilayer polymer particles,
And a molding use of the resin composition.

[0005]

Means for Solving the Problems Some of the present inventors have made various attempts to provide a multilayer-structured polymer particle capable of providing a molded article having excellent elastic recovery (low permanent set characteristics). As a result of the examination, the molecular weight of the thermoplastic resin component constituting the outermost layer of the multilayer polymer particles, and the average particle diameter of the particles were controlled to a specific composition range, and the multilayer polymer particles composed of at least two layers. Provided that a molded article having excellent elastic recovery (low permanent set properties) can be obtained, and a patent application was filed earlier (Japanese Patent Application No. 10-1).
No. 16024). As a result of further intensive studies, the present inventors have found that when the layer structure of the particles is controlled within specific conditions, excellent elastic recovery (low permanent set properties), moderate flexibility and good other properties are obtained. The inventors have found that multi-layered polymer particles capable of providing a molded article having well-balanced mechanical properties are provided, and have further studied, and completed the present invention.

According to the present invention, one of the above problems is:

(1) It has a rubber component layer (I) at the innermost part,
Multilayer polymer particles comprising at least three polymer layers, having a rubber component layer (II) in the innermost adjacent part and a thermoplastic resin component layer (III) in the outermost part;

(2) The rubber component layers (I) and (II)
50 to 95% by weight of an acrylate ester, other monofunctional monomers 4 copolymerizable with the acrylate ester
9.99-0% by weight, and 0.01-1 polyfunctional monomer
A polymer layer formed by copolymerization of a monomer mixture (i) and (ii) consisting of 0% by weight;

(3) The content (% by weight) of the acrylate in the monomer mixture (i) is determined based on the monomer mixture (i).
lower than the acrylate content (% by weight) in i);

(4) The thermoplastic resin component layer (III) comprises:
40 to 99% by weight of methacrylate and 60 to 1% by weight of other monomer copolymerizable with the methacrylate
A polymer layer formed by copolymerization of a monomer mixture (iii) consisting of:

(5) The number average molecular weight of the polymer constituting the thermoplastic resin component layer (III) measured by the GPC method is 30,000 or less;

(6) The ratio of the sum of the weights of the rubber component layers (I) and (II) to the weight of the thermoplastic resin component layer (III) is represented by [(I) + (II)] / (III). , 30
/ 70 to 90/10;

(7) The ratio of the weight of the rubber component layer (I) to the weight of the rubber component layer (II) is in the range of 5/95 to 95/5 in (I) / (II); And,

(8) the average particle size is 150 nm or less;

The problem is solved by providing a multi-layered polymer particle characterized by the following.

According to the present invention, one of the above-mentioned problems is solved by providing a molding material comprising the above-mentioned multilayer polymer particles; and a film or sheet comprising the above-mentioned multilayer polymer particles. You.

According to the present invention, one of the above-mentioned objects is attained by providing a resin composition comprising the above-mentioned multilayer polymer particles and a synthetic resin.

Further, according to the present invention, one of the above problems is solved by providing a molding material comprising the above resin composition; and a film or sheet comprising the above resin composition, respectively.

[0019]

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 composed of three or more polymer layers, have a rubber component layer (I) at the innermost part, and are located adjacent to the innermost part so as to cover the outer surface. The portion has a rubber component layer (II) and the outermost portion has a thermoplastic resin component layer (III).

The layer (I) in the multilayer polymer particles according to the present invention comprises 50 to 95% by weight of an acrylate ester and another monofunctional monomer 4 copolymerizable with the acrylate ester.
9.99-0% by weight, and 0.01-1 polyfunctional monomer
It is a polymer layer having rubber elasticity formed by copolymerization of a monomer mixture (i) consisting of 0% by weight. Further, the layer (II) comprises 50 to 95% by weight of an acrylate ester, 49.99 to 0% by weight of another monofunctional monomer copolymerizable with the acrylate ester, and 0% by weight of a polyfunctional monomer. .01-
It is a polymer layer having rubber elasticity formed by copolymerization of a monomer mixture (ii) consisting of 10% by weight.

Specific examples of the acrylate used for forming the layer (I) and the layer (II) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylate. Acrylics such as butyl, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate Acid alkyl esters; esters of acrylic acid such as phenyl acrylate with phenols; esters of acrylic acid such as benzyl acrylate with aromatic alcohols; Among these acrylates, n-butyl acrylate is preferred. The acrylate is used alone or in an amount of 50 to 95% by weight based on the monomer mixture (i) and (ii) used to form the layer (I) and the layer (II), respectively. Used as a mixture of more than one species. If the amount of the acrylate is less than 50% by weight, the rubber elastic modulus of the multilayer structure polymer particles will decrease, and if it exceeds 95% by weight, the multilayer structure polymer particles alone or a mixture thereof with the synthetic resin will not be obtained. In some cases, the mechanical properties of a molded product obtained by molding the resin composition are insufficient.

The polyfunctional monomer used to form each of the layer (I) and the layer (II) has a carbon atom in the molecule.
A monomer having two or more carbon double bonds, for example,
Esters of unsaturated carboxylic acids such as acrylic acid, methacrylic acid and cinnamic acid with unsaturated alcohols such as allyl alcohol and methallyl alcohol, or glycols such as ethylene glycol and butanediol; phthalic acid, terephthalic acid, isophthalic acid and maleic acid Esters of a dicarboxylic acid such as an acid and the above-mentioned unsaturated alcohol, and the like.Specifically, allyl acrylate, methallyl acrylate, allyl methacrylate, methacrylic methallyl, allyl cinnamate,
Methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene di (meth) acrylate, tetramethylene di (meth) acrylate, hexamethylene di (meth) acrylate, etc. No. Among these polyfunctional monomers, allyl methacrylate is particularly preferred.
The “(meth) acrylic acid” means a general term for “acrylic acid” and “methacrylic acid”. The polyfunctional monomer is used in an amount of 0.01 to 10% by weight based on the monomer mixture (i) and (ii) used to form the layer (I) and the layer (II), respectively. , Alone or as a mixture of two or more. The amount of polyfunctional monomer is 1
If it is more than 0% by weight, the polymer particles having a multilayer structure do not show rubber elasticity and the elastic recovery becomes insufficient. This is not preferable because the layer structure cannot be formed.

In order to form the layers (I) and (II), respectively, other monofunctional monomers copolymerizable with the acrylate ester besides the acrylate ester and the polyfunctional monomer are used. Can be used together. Examples of the other monofunctional monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, and methacrylic acid. Octyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, etc .; esters of methacrylic acid and phenols such as phenyl methacrylate And methacrylic acid esters such as esters of methacrylic acid such as benzyl methacrylate and aromatic alcohols are typical. In addition, styrene, α-methylstyrene, 1-vinylna Aromatic vinyl monomer such as taren, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene, etc. Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; butadiene, isoprene, 2,3-pentadiene, 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-1,3-hexadiene, 1,
Examples include conjugated diene monomers such as 3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, cyclopentadiene, chloroprene, and myrcene. If necessary, these monomers may be used in an amount of 49.99% by weight or less based on the monomer mixtures (i) and (ii) used to form the layers (I) and (II), respectively. In the ratio, they can be used alone or in combination of two or more. When the ratio of the other monofunctional monomer is 4
If it exceeds 9.99% by weight, the weather resistance of the multilayer structure polymer particles becomes insufficient.

In order to make excellent elastic recovery compatible with good flexibility and good mechanical properties in a molded article obtained by molding a resin composition of a multilayered polymer particle alone or a synthetic resin and the same. Regarding the layer (I) and the layer (II) of the multilayer polymer particles of the present invention, the content (% by weight) of the acrylate in the monomer mixture (i) is the same as that in the monomer mixture (ii). It is important that the content (% by weight) of the acid ester is lower. Acrylic ester content in monomer mixture (i) (% by weight)
Is not less than the content (% by weight) of the acrylate in the monomer mixture (ii),
It is generally difficult to combine excellent elastic recovery with moderate flexibility and good mechanical properties. In order to make the effect of the present invention more remarkable, the content (% by weight) of the acrylate in the monomer mixture (i)
And the content (% by weight) of the acrylate in the monomer mixture (ii) [(ii) (unit:% by weight) −
(I) (unit:% by weight)] is preferably 3% by weight or more.

The layer (III) in the multilayer polymer particles according to the present invention comprises from 40% by weight to 99% by weight of methacrylate.
A thermoplastic polymer layer formed by copolymerization of a monomer mixture (iii) consisting of 60% by weight and 60-1% by weight of another monomer copolymerizable therewith. When the content of the methacrylate in the monomer mixture (iii) is less than 40% by weight, the weather resistance of the multilayer polymer particles becomes insufficient, and when it is more than 99% by weight, the heat resistance becomes insufficient.

Specific examples of the methacrylate used to form the layer (III) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. , Pentyl methacrylate,
Hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate,
Examples include palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate, benzyl methacrylate, and the like, with methyl methacrylate being preferred. Specific examples of other copolymerizable monomers used to form the layer (III) include methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic acid Dodecyl,
Acrylic acid alkyl esters such as octadecyl acrylate; styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene,
-Cyclohexylstyrene, 4-dodecylstyrene, 2
Aromatic vinyl monomers such as -ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; maleimide, N-methylmaleimide Maleimide monomers such as N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide; Examples include the polyfunctional monomers shown in the above examples. 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,
It is important that the number average molecular weight of the copolymer constituting the outermost layer (III) is 30,000 or less based on measurement by GPC (gel permeation chromatography). When the number average molecular weight exceeds 30,000, the elastic recovery property of the molded article obtained by molding the multilayer structure polymer particles alone or a resin composition of the same and the synthetic resin becomes insufficient, and the melt fluidity further decreases. In some cases. The lower limit of the number average molecular weight is not necessarily strictly limited, but it is preferable that the number average molecular weight does not fall below 1,000 from the viewpoint of the passability of the production process. It is particularly preferred that the number average molecular weight is in the range of 3,000 to 25,000 from the viewpoint of achieving both elastic recovery and passability in the production process.

In the multilayer polymer particles of the present invention, the layers (I) and (II) are composed of a polymer component having rubber elasticity, and the layer (III) is composed of a polymer component having thermoplasticity. As described above, the conditions may be appropriately selected within the ranges of the types and the usage ratios of the monomers as described above. However, when importance is placed on transparency of the molded article composed of the multi-layered polymer particles, between the adjacent polymer layers in the multi-layered polymer particles [for example, when the multi-layered polymer particles have a three-layered structure] , The layer (I) and the layer (II)
, And between the layer (II) and the layer (III)], it is preferable to appropriately select the type and the use ratio of the monomer for forming each layer.

In the multilayer polymer particles of the present invention,
The ratio of the sum of the weights of the rubber component layers (I) and (II) to the weight of the thermoplastic resin component layer (III) is [(I) + (I
I)] / (III), 30/70 to 90/10
Within the range. When the ratio of the sum of the weights of the layer (I) and the layer (II) is smaller than this range, elastic recovery and flexibility in a molded article obtained by molding the multilayer structure polymer particles alone or a resin composition thereof and a synthetic resin are obtained. On the other hand, if the ratio of the sum of the weights of the layers (I) and (II) is larger than this range, it is difficult to form the layer structure in a perfect form, and the melt fluidity is extremely reduced. Therefore, molding and kneading with another synthetic resin become difficult. In order to make the effect of the present invention more remarkable, the sum of the weights of the rubber component layers (I) and (II) and the thermoplastic resin component layer (III)
Is preferably in the range of 60/40 to 90/10 in [(I) + (II)] / (III). In the multilayer polymer particles of the present invention, the ratio of the weight of the rubber component layer (I) to the weight of the rubber component layer (II) is 5/95 to 9 in (I) / (II).
It is within the range of 5/5. When the ratio of the weight of the rubber component layer (I) to the weight of the rubber component layer (II) is out of this range,
In general, it is difficult to combine good elastic recovery with moderate flexibility and good other mechanical properties.

The multi-layered polymer particles of the present invention comprise an innermost rubber component layer (I) and an adjacent rubber component layer (I).
The basic structure is composed of three layers of I) and the outermost thermoplastic resin component layer (III), and one or more arbitrary polymer layers are interposed between the layers (II) and (III). You may. However, for the purpose of making the effect of the present invention particularly remarkable, the sum of the weights of the rubber component layer (I), the rubber component layer (II) and the thermoplastic resin component layer (III) is determined by the total weight of the multilayer polymer particles. It is preferably 80% or more based on the weight, and more preferably the multilayer polymer particles are composed of only the rubber component layer (I), the rubber component layer (II) and the thermoplastic resin component layer (III). .

The average particle size of the multilayer polymer particles of the present invention is 150 nm or less. If it is larger than 150 nm, the elastic recovery becomes insufficient, and the melt fluidity may be poor. The lower limit of the average particle diameter is not particularly limited, but from the viewpoint of easily forming a predetermined layer structure of the multilayer polymer particles, the average particle diameter is 30.
It is preferably at least nm.

The polymer particles having a multilayer structure of the present invention can be prepared by a polymerization reaction operation for forming a rubber layer component (I) and a rubber layer component (II) in accordance with a known production method for producing multilayer polymer particles. ) And a polymerization reaction operation for forming a predetermined polymer layer, including a polymerization reaction operation for forming the thermoplastic resin component layer (III), in a predetermined order. Can be manufactured by sequentially forming layers from the center toward the outside. However, in that case, the following points (1)-
It is necessary to pay attention to (7).

(1) Polymerization reaction operations (a) and (b) for forming rubber component layers (I) and (II), respectively
In the above, 50 to 95% by weight of an acrylate ester, another monofunctional monomer 4 copolymerizable with the acrylate ester
9.99-0% by weight, and 0.01-1 polyfunctional monomer
Copolymerizing the monomer mixtures (i) and (ii) consisting of 0% by weight.

(2) The content (% by weight) of the acrylate in the monomer mixture (i) is
It is set to be lower than the content (% by weight) of the acrylate in i).

(3) In the polymerization reaction operation (c) for forming the thermoplastic resin component layer (III), 40 to 99% by weight of a methacrylic acid ester and other monomers copolymerizable with the methacrylic acid ester Copolymerizing a monomer mixture (iii) consisting of 60 to 1% by weight.

(4) In the above polymerization reaction operation (c),
The polymer constituting the layer (III) has a number average molecular weight of 30,
Control the reaction conditions to be less than 000.

(5) The ratio of the sum of the weights of the monomer mixture (i) and the monomer mixture (ii) to the weight of the monomer mixture (iii) is [(i) + (ii)] / (Iii) 3
Set to be in the range of 0/70 to 90/10.

(6) The ratio of the weight of the monomer mixture (i) to the weight of the monomer mixture (ii) is in the range of 5/95 to 95/5 in (i) / (ii). To set

(7) The average particle size of the multilayer polymer particles at the time when all the polymerization reaction operations are completed is 150 n
m.

The above polymerization method is not particularly limited. For example, an emulsion polymerization method, a suspension polymerization method, a suspension polymerization method, or the like according to a known polymerization method for producing ordinary multilayer polymer particles.
A bulk polymerization method, a solution polymerization method, or a combination thereof can be employed.

For example, in the emulsion polymerization method, the multilayer structure polymer particles of the present invention can be obtained by performing polymerization for forming each layer according to known means. The temperature of the emulsion polymerization is not necessarily limited, but a general range is from 0 to 100 ° C. Examples of the emulsifier used here include aliphatic alkali metal salts such as sodium oleate, sodium laurate and sodium stearate; sulfate salts of aliphatic alcohols such as sodium lauryl sulfate; rosinate salts such as potassium rosinate; Metal salts of alkyl aryl sulfonic acids such as sodium dodecyl benzene sulfonate; phosphoric acid esters; and the like, and these are used in combination of one or more kinds. As the polymerization initiator used in the emulsion polymerization, a radical polymerization initiator is generally used. As specific examples of the radical polymerization initiator, persulfates such as potassium persulfate and peroxides such as benzoyl peroxide can be used alone. Further, a redox initiator obtained by combining a peroxide such as cumene hydroperoxide and a reducing agent such as a ferrous salt can be used.

As described above, a predetermined amount of a predetermined monomer mixture is sequentially polymerized in accordance with a known emulsion polymerization method, whereby a predetermined polymer layer is formed stepwise from the center of the particles to the outside. The outermost layer (II
In order to control the number average molecular weight of the polymer constituting the layer (III) to be 30,000 or less in the polymerization reaction using the monomer mixture (iii) for forming I) , A molecular weight modifier in a monomer mixture (ii)
It is preferred to use i in a ratio that falls within the range of 0.4 to 10% by weight with respect to i). When producing ordinary multi-layer polymer particles, the amount of the molecular weight regulator used in the polymerization reaction for forming the outermost thermoplastic resin component layer is generally from 0 to 0. It is about 3% by weight. When the amount of the molecular weight modifier used is less than 0.4% by weight based on the monomer, it is generally difficult to control the number average molecular weight of the formed polymer to 30,000 or less. For the purpose of producing the multi-layered polymer particles of the present invention, the amount of the molecular weight regulator is at most 10 based on the above-mentioned standard.
% By weight is sufficient and even if you use more,
There is no longer any further improvement in the effect of imparting elastic recovery, and rather, the residual amount of the molecular weight modifier in the multilayer polymer particles is undesirably increased.

Specific examples of the molecular weight regulator include mercaptans such as n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and mercaptoethanol; terpinolene, dipentene, t-terpinene and a small amount. A terpene mixture of cyclic terpenes; halogenated hydrocarbons such as chloroform and carbon tetrachloride. Of these, alkyl mercaptans such as n-octyl mercaptan are preferred.

Since the average particle size of the multilayer polymer particles obtained by emulsion polymerization is influenced by polymerization conditions such as the amount of the emulsifier, the final multilayer structure weight can be easily determined by appropriately selecting these conditions. The average particle diameter of the coalesced particles can be controlled to 150 nm or less.

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, and a freeze coagulation method. Etc. can be adopted. In addition,
The multilayer-structured polymer particles obtained by separation may be partially fused to each other in the outermost layer made of a thermoplastic resin component.

The multi-layer polymer particles of the present invention can be subjected to thermal molding because the outermost layer has thermoplasticity and excellent melt fluidity, and can be subjected to, for example, 180 to 280.
Extrusion molding at ℃, injection molding, hollow molding, calendar molding,
By molding methods such as compression molding, vacuum molding, foam molding, etc., it can be molded into a molded article of any shape such as powder, pellet, plate, film or sheet, pipe, hollow, box, etc. . Since the molded article has excellent elastic recovery properties, it is suitably used for applications such as soft members for automobile interiors, packaging films, and desk mats.

The performance of the synthetic resin can be imparted by adding another synthetic resin to the multilayer polymer particles of the present invention. In the resin composition comprising the multilayer structure polymer particles and another synthetic resin, further synthesizing while taking advantage of the excellent elastic recovery property of the multilayer structure polymer particles of the present invention, moderate flexibility and good mechanical properties. For the purpose of expressing preferable performance derived from the resin, it is desirable that the weight ratio of the multilayer structure polymer particles to the synthetic resin is in the range of 50/50 to 95/5 in the multilayer structure polymer particles / synthetic resin. . However, if it is sufficient to at least partially express the performance derived from the multilayer structure polymer particles in the resin composition composed of the multilayer structure polymer particles and another synthetic resin, the content of the multilayer structure polymer particles may be included. The mixing ratio of the two can be appropriately set within a range where the ratio is 5% by weight or more and the content of the synthetic resin is 95% by weight or less.

In the resin composition of the present invention comprising the polymer particles having a multilayer structure and another synthetic resin, the 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 polyethylene, polypropylene, polybutene-1, and poly-4.
Polyolefin resins such as methylpentene-1 and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, ABS, AES, AAS, ACS, M
Styrene resins such as BS; polymethyl methacrylate;
Acrylic resin such as methyl methacrylate-styrene copolymer, other acrylic multi-layer polymer particles, etc .; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate; Polyamide resin such as nylon 6, nylon 66, polyamide elastomer; Polycarbonate; Vinyl; polyvinylidene chloride; polyacetal; polyvinylidene fluoride; polyurethane; modified polyphenylene ether; polyphenylene sulfide; Specific examples of the thermosetting resin include an epoxy resin, an unsaturated polyester, a phenol resin, a urea resin, and a melamine resin.

Known additives (eg, rubber, lubricant, antioxidant, plasticizer) may be added to the resin composition comprising the polymer particles having a multilayer structure of the present invention and a synthetic resin within a range that does not impair the effects of the present invention. , A light stabilizer, a colorant, an antistatic agent, a flame retardant, etc.), a filler (a fiber reinforcing agent such as glass fiber, an inorganic filler, etc.) and the like.

When the synthetic resin is a thermoplastic resin, the resin composition containing the polymer particles having a multilayer structure and the synthetic resin of the present invention is used, for example, in the case of the polymer particles having a multilayer structure, a synthetic resin, and if desired. It can be produced by thoroughly mixing other components under melt-kneading conditions. Further, when the synthetic resin is a thermosetting resin, for example, using a solvent or the like as necessary before curing the thermosetting resin, the multilayer structure polymer particles, the thermosetting resin, and used as desired A resin composition can be manufactured by mixing and casting other components.

As a method for molding and processing the resin composition comprising the multilayer structure polymer particles and the synthetic resin of the present invention, when the synthetic resin is a thermoplastic resin, thermal molding is possible, for example, at 180 to 280 ° C. Molding method such as extrusion molding, injection molding, hollow molding, calendar molding, compression molding, vacuum molding, foam molding, etc., powder, pellet, plate, film or sheet, pipe, hollow, box It can be formed into an arbitrary shaped article. When the synthetic resin is a thermosetting resin, it can be molded at room temperature or lower, and can be formed into a powder by a molding method such as extrusion molding, injection molding, hollow molding, calendar molding, compression molding, vacuum molding, or foam molding. , Pellets, plates, films or sheets, pipes, hollows, and boxes.

The molded article comprising the resin composition comprising the multi-layered polymer particles of the present invention and the synthetic resin is characterized by the properties of the synthetic resin and the appropriate flexibility and elastic recovery derived from the multi-layered polymer particles. Since it exhibits its characteristics, it is particularly suitably used for applications such as door packing for indoor use and cushions for covering handrails on stairs.

[0054]

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 average particle size of the polymer particles having a multilayer structure was measured by a dynamic scattering method using a laser particle size analyzer PAR-III (manufactured by Otsuka Electronics Co., Ltd.) using a sample collected from the latex after completion of the polymerization. And analyzed by the cumulant method.

The tensile strength at break, tensile elongation at break, stress at 100% elongation (100% modulus), and permanent elongation were measured according to JIS K 6301 using Autograph AG-2000B (manufactured by Shimadzu Corporation). did.

The compression set was measured using a constant strain compression molding machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to JIS K6301.

The hardness was measured using an A-type hardness tester (manufactured by Oscar) in accordance with JIS K6301.

The number average molecular weight of the polymer component constituting the outermost layer can be determined by a GPC method using a solution obtained by sufficiently stirring a sample of multilayer polymer particles in toluene at room temperature and then centrifuging. Was measured by

Example 1 (Production Example of Multilayer Structure Polymer Particles) Under a nitrogen atmosphere, 200 parts by weight of distilled water, Neoperex F-25 as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel. 0.6 part by weight (manufactured by Kao) and 0.1 part by weight of sodium carbonate were added, and the mixture was heated to 80 ° C. and uniformly dissolved. Then, at the same temperature, after adding 0.05 parts by weight of potassium peroxodisulfate, the acrylic acid n
-Butyl 30 parts by weight, methyl methacrylate 13.5 parts by weight, styrene 6.5 parts by weight, allyl methacrylate 0.2
Parts by weight, and Adekacol CS-141 as an emulsifier
0.25 parts by weight of E (manufactured by Asahi Denka) was dropped from the dropping funnel over 1 hour. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. Next, after adding 0.025 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 20 parts by weight of n-butyl acrylate, 0.5 part by weight of methyl methacrylate, 4.5 parts by weight of styrene, 4.5 parts by weight of methacryl 0.1 parts by weight of allyl acid and 0.125 parts by weight of Adekacol CS-141E (manufactured by Asahi Denka) as an emulsifier were added dropwise from a dropping funnel over 30 minutes. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. Further, after adding 0.025 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, methyl methacrylate 2
3.75 parts by weight, 1.25 parts by weight of methyl acrylate, n
-0.25 parts by weight of octyl mercaptan and 0.1 of Adekacol CS-141E (manufactured by Asahi Denka) as an emulsifier
25 parts by weight were dropped from the dropping funnel over 30 minutes.
After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed, and the polymerization was terminated. The average particle size of the multilayer polymer particles in the obtained latex was 104 nm. This latex 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 40 ° C. 60 ° C
And dried under reduced pressure for 2 days to obtain aggregated powdery three-layer type multilayer structure polymer particles [A-1]. A sheet was prepared from the obtained powdery A-1 at 230 ° C. using a compression molding machine, and various measurements were performed. Table 1 shows the obtained results.

Example 2 (Production Example of Multilayered Polymer Particles) Polymerization was carried out in the same manner as in Example 1 except that the amount of n-octyl mercaptan was changed from 0.25 parts by weight to 0.125 parts by weight. By performing each operation of reaction, aggregation, and drying, aggregated powdery three-layer type polymer particles [A-2] were obtained. The average particle size of the multilayer polymer particles in the latex obtained after the third stage polymerization was 95 nm. A sheet was prepared from the obtained powdery A-2 at 230 ° C. using a compression molding machine, and various measurements were performed. Table 1 shows the obtained results.

Example 3 (Production Example of Multilayer Polymer Particles) Under a nitrogen atmosphere, a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel was charged with 200 parts by weight of distilled water and Neoperex F-25 as an emulsifier. 0.6 part by weight (manufactured by Kao) and 0.1 part by weight of sodium carbonate were added, and the mixture was heated to 80 ° C. and uniformly dissolved. Then, at the same temperature, after adding 0.047 parts by weight of potassium peroxodisulfate, 28.2 parts by weight of n-butyl acrylate and methyl methacrylate 12.
69 parts by weight, 6.11 parts by weight of styrene, 0.188 parts by weight of allyl methacrylate, and 0.235 parts by weight of Adecacol CS-141E (manufactured by Asahi Denka) as an emulsifier were added dropwise from a dropping funnel over 57 minutes. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. Subsequently, potassium peroxodisulfate was added to the obtained copolymer latex in an amount of 0.1%.
After adding 023 parts by weight, n-butyl acrylate 18.
4 parts by weight, 0.46 parts by weight of methyl methacrylate, 4.14 parts by weight of styrene, 0.092 parts by weight of allyl methacrylate, and ADECACOL CS-141E as an emulsifier
0.115 parts by weight (manufactured by Asahi Denka) was dropped from the dropping funnel over 28 minutes. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. Further, after adding 0.03 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 28.5 parts by weight of methyl methacrylate, 1.5 parts by weight of methyl acrylate, 0.3 part of n-octyl mercaptan
Parts by weight, and Adekacol CS-141 as an emulsifier
0.15 parts by weight of E (manufactured by Asahi Denka) was dropped from the dropping funnel over 36 minutes. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed, and the polymerization was terminated. The average particle diameter of the multilayer polymer particles in the obtained latex is 100 n.
m. This latex 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 40 ° C. It was dried under reduced pressure at 60 ° C. for 2 days to obtain aggregated powdery three-layer type multilayer structure polymer particles [A-3]. From the obtained powdery A-3, using a compression molding machine, 230
A sheet was prepared at ℃, and various measurements were performed. Table 1 shows the obtained results.

Example 4 (Production Example of Resin Composition of Multilayer Structure Polymer Particles and Synthetic Resin) Multilayer structure polymer particles [A-1] 90 obtained in Example 1
Parts by weight and acrylic resin (Kuraray parapet G) 10
The parts by weight were put in a tumbler and mixed. After that, 45m
The mixture was continuously fed to a twin-screw extruder having an mφ of 230 ° C. and an extruder temperature of 230 ° C. to prepare pellets of the resin composition [B-1] in which the multilayer polymer particles [A-1] and the acrylic resin were uniformly mixed. A sheet was prepared from the obtained pellet B-1 at 230 ° C. using a compression molding machine, and various measurements were performed. Table 1 shows the obtained results.

Comparative Example 1 Under a nitrogen atmosphere, 200 parts by weight of distilled water, 0.6 parts by weight of Neoperex F-25 (manufactured by Kao) as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel. 0.1 parts by weight of sodium carbonate was added, and the mixture was heated to 80 ° C. and uniformly dissolved. Then, at the same temperature, after adding 0.05 parts by weight of potassium peroxodisulfate, the acrylic acid n
-Butyl 33.5 parts by weight, methyl methacrylate 9.5 parts by weight, styrene 7 parts by weight, allyl methacrylate 0.2 parts by weight, and ADECACOL CS-141E as an emulsifier
0.25 parts by weight (manufactured by Asahi Denka) was dropped from the dropping funnel over 1 hour. After the completion of dropping, the reaction was continued for another hour,
Gas chromatography confirmed that all of the monomers had been consumed. Next, after adding 0.025 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 16.75 parts by weight of n-butyl acrylate, 4.75 parts by weight of methyl methacrylate, and 3.5 parts by weight of styrene , 0.1 parts by weight of allyl methacrylate and 0.125 parts by weight of Adekacol CS-141E (manufactured by Asahi Denka) as an emulsifier were added dropwise from a dropping funnel over 30 minutes. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. further,
After adding 0.025 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, methyl methacrylate 2
3.75 parts by weight, 1.25 parts by weight of methyl acrylate, n
-0.25 parts by weight of octyl mercaptan and 0.1 of Adekacol CS-141E (manufactured by Asahi Denka) as an emulsifier
25 parts by weight were dropped from the dropping funnel over 30 minutes.
After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed, and the polymerization was terminated. The average particle size of the multilayer polymer particles in the obtained latex was 97 nm. This latex 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 40 ° C. The polymer was dried under reduced pressure at 60 ° C. for 2 days to obtain two-layered multi-layer polymer particles [C-1] in the form of aggregated powder. A sheet was prepared from the obtained powdered C-1 at 230 ° C. using a compression molding machine, and various measurements were performed. Table 1 shows the obtained results.

Comparative Example 2 Under a nitrogen atmosphere, 200 parts by weight of distilled water, 0.6 parts by weight of Neoperex F-25 (made by Kao) as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel. 0.1 parts by weight of sodium carbonate was added, and the mixture was heated to 80 ° C. and uniformly dissolved. Next, at the same temperature, after adding 0.025 parts by weight of potassium peroxodisulfate, 20 parts by weight of n-butyl acrylate, 0.5 part by weight of methyl methacrylate, 4.5 parts by weight of styrene, and 0.4 parts by weight of allyl methacrylate were added. 1
Parts by weight, and Adekacol CS-141 as an emulsifier
E (made by Asahi Denka) 0.125 parts by weight from the dropping funnel 30
It was added dropwise over a period of minutes. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. Next, after adding 0.05 parts by weight of potassium peroxodisulfate to the obtained copolymer latex, 30 parts by weight of n-butyl acrylate, 13.5 parts by weight of methyl methacrylate, 6.5 parts by weight of styrene, and 0.2 parts by weight of allyl acid and 0.25 parts by weight of Adekacol CS-141E (manufactured by Asahi Denka) as an emulsifier were added dropwise from a dropping funnel over 1 hour. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed. Further, potassium peroxodisulfate was added to the obtained copolymer latex in an amount of 0.1%.
After adding 025 parts by weight, methyl methacrylate 23.7 was added.
5 parts by weight, 1.25 parts by weight of methyl acrylate, 0.25 parts by weight of n-octyl mercaptan, and 0.125 parts by weight of Adekacol CS-141E (manufactured by Asahi Denka) as an emulsifier were dropped from the dropping funnel over 30 minutes. did. After the completion of the dropwise addition, the reaction was further continued for 1 hour, and it was confirmed by gas chromatography that all the monomers had been consumed, and the polymerization was terminated. The average particle diameter of the multilayer polymer particles in the obtained latex was 106 nm. This latex 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 40 ° C. It was dried under reduced pressure at 60 ° C. for 2 days to obtain aggregated powdery three-layer type multilayer polymer particles [C-2]. From the obtained powdered C-2, a sheet was prepared at 230 ° C. using a compression molding machine, and various measurements were performed. Table 1 shows the obtained results.

[0066]

[Table 1]

From the above Table 1, it can be seen that the multilayer structured polymer particles according to the present invention obtained in Examples 1 to 3 have excellent elastic recovery as represented by a low tensile elongation of about 25% or less, for example. Not only that, it has good flexibility as represented by a moderate hardness (JIS A) in the range of about 70 to 90, for example, and has a high tensile strength at break of about 10 MPa or more, and about 5 MPa or more. It has excellent mechanical properties as represented by a high 100% modulus and a tensile elongation at break of about 200% or more. Also, in Example 4, the resin composition obtained by blending the multilayer polymer particles according to the present invention with a synthetic resin in Example 4 also balances excellent elastic recovery, good flexibility and good other mechanical properties. You can see that they have a good combination. On the other hand, the multilayered polymer particles of Comparative Example 1, which is different from the present invention in that it has a two-layer structure having only one rubber component layer, and a single layer for forming the innermost rubber component layer. In the multilayer polymer particles of Comparative Example 2, which is different from the present invention in that the acrylate content in the monomer mixture is not lower than the acrylate content in the rubber component layer in the adjacent part, the outermost Although the number average molecular weight of the polymer constituting the thermoplastic resin layer is 30,000 or less, the elastic recovery is good, but the flexibility is inferior to that of the multilayer polymer particles of Examples. (Too hard or too soft) and poor mechanical properties.

[0068]

As described above, according to the present invention, a multilayer polymer particle having not only excellent elastic recovery properties but also appropriate flexibility and excellent mechanical properties is provided. The multilayer structure polymer particles can be easily molded, and the resulting molded product exhibits the above-mentioned excellent performance, and thus is useful as a molding material. Further, by combining the multilayer polymer particles with a synthetic resin, it is possible to obtain a resin composition useful as a molding material.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazutoshi Terada 41 Miyukigaoka, Tsukuba, Ibaraki Prefecture Inside Kuraray Co., Ltd. (72) Inventor Tatsuya Naruse 2-28 Kurashiki-cho, Nakajo-cho, Kitakanbara-gun, Niigata Kuraray Co., Ltd. (72) Inventor Takao Hiraba 2-28 Kurashiki-cho, Nakajo-cho, Kitakanbara-gun, Niigata F-term in Kuraray Co., Ltd. (Reference) BG04W BG06X BN06X BN07X BN15X BN211 CF06X CF07X GG00 4J026 AA17 AA45 AA46 AC19 BA27 BA28 BB03 BB04 BB08 DA04 DB04 DB13 FA07

Claims (8)

[Claims] (1) A rubber component layer (I) at the innermost portion, a rubber component layer (II) at an adjacent portion of the innermost portion, and a thermoplastic resin component layer (III) at the outermost portion. (2) each of the rubber component layers (I) and (II) comprises 50 to 95% by weight of an acrylate ester, Other monofunctional monomers copolymerizable with 49.99 to 0
A polymer layer formed by copolymerization of a monomer mixture (i) and (ii) consisting of 0.01% by weight and 0.1 to 10% by weight of a polyfunctional monomer; (3) monomer mixture The content (% by weight) of the acrylate in (i) is lower than the content (% by weight) of the acrylate in the monomer mixture (ii); (4) the thermoplastic resin component layer (III) A polymer layer formed by copolymerization of a monomer mixture (iii) comprising 40 to 99% by weight of a methacrylate and 60 to 1% by weight of another monomer copolymerizable with the methacrylate; (5) The number average molecular weight of the polymer constituting the thermoplastic resin component layer (III) measured by the GPC method is 30,
(6) The ratio of the sum of the weights of the rubber component layers (I) and (II) to the weight of the thermoplastic resin component layer (III) is [(I) +
(II)] / (III), 30/70 to 90 /
(7) The ratio of the weight of the rubber component layer (I) to the weight of the rubber component layer (II) is 5/95 to (I) / (II).
(8) an average particle diameter of 150 nm or less; 2. Rubber component layer (I), rubber component layer (II)
2. The multilayer polymer particles according to claim 1, wherein the sum of the weight of the thermoplastic resin component layer (III) and the total weight of the multilayer polymer particles is 80% or more. 3. An acrylic acid ester for forming each of the rubber component layers (I) and (II) is made of acrylic acid n
3. The multilayer polymer particle according to claim 1, which is -butyl. 4. 4. A molding material comprising the multilayer polymer particles according to claim 1. 5. A film or sheet comprising the multilayer polymer particles according to claim 1. 6. A resin composition comprising the multilayer polymer particles according to claim 1, 2 or 3, and a synthetic resin. 7. A molding material comprising the resin composition according to claim 6. 8. A film or sheet comprising the resin composition according to claim 6.