JPH08231770A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE: To provide a flexible elastomer composition excellent in tensile elongation set and compressive resistance. CONSTITUTION: This thermoplastic elastomer composition comprises (A) 30-90wt.% of a thermoplastic copolyester elastomer or thermoplastic copolyamide elastomer and (B) 70-10wt.% of a core-shell type rubber composed of crosslinked rubbery elastomer core layer <=25 deg.C in glass transition temperature and copolymer shell layer <=25 deg.C in glass transition temperature containing in one molecule epoxy group and/or carboxyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition which is flexible and has excellent tensile permanent elongation and compression resistance.

[0002]

2. Description of the Related Art Copolyester elastomers are multiblock copolymers composed mainly of polyester and polyether as repeating units, and copolyamide elastomers are multiblock copolymers composed mainly of polyamide and polyether or polyester as repeating units. And all of them are elastomers having appropriate flexibility. However, these copolyester elastomers and copolyamide elastomers have high hardness as elastomers and are inferior in flexibility and strain recovery in order to be used in the rubbery region. In order to improve this, it is common practice to increase the content of soft segments in these copolyelastomers. However, when the content of the soft segment in these copolyelastomers is increased, there is a drawback that the melting point of the elastomer is lowered and the high temperature usable temperature range is lowered. As another method of softening, a method of adding a softening agent such as a plasticizer is known. However, this method has a drawback that the softener is extracted or volatilized during use and is hardened again.

As a method for solving the above problems, there is known a method of mixing a rubber with the above copolyelastomer.
Japanese Patent Application Laid-Open No. 1-266154 discloses a composition obtained by blending an acrylic rubber in which 1 to 5% of a reactive curable monomer is copolymerized with a copolyester elastomer, wherein the acrylic rubber is cross-linked. Uncrosslinked compositions are disclosed. However, this uncrosslinked composition is inferior in compression set, and when a typical crosslinked system of acrylic rubber as exemplified in the crosslinked composition, for example, a quaternary ammonium salt is used, a copolyester is used. It has the drawback of degrading the elastomer and degrading the performance of the molded product.

JP-A-5-25374 and JP-A-5-25
No. 375 describes that when a thermoplastic copolyester elastomer or a thermoplastic copolyamide elastomer is mixed with an epoxy group-containing (meth) acrylate copolymer rubber, 1
Disclosed is a thermoplastic elastomer which is crosslinked by a compound having at least two carboxyl groups in the molecule and / or an isocyanuric acid compound and an imidazole compound. However, when the epoxy group content is increased in order to improve the compression set resistance, the tensile elongation at break is remarkably reduced, and further improvement is desired.

According to the research conducted by the inventors, in order to obtain a thermoplastic elastomer composition excellent in tensile permanent elongation and compression set resistance by mixing a copolyester elastomer with rubber to soften it, the rubber particles should be copolyester. It is necessary to finely disperse in the elastomer matrix and to tightly crosslink the rubber particles. That is, to create a structural composition in which finely crosslinked rubber particles are dispersed in a copolyelastomer matrix. This structure is also achieved by forming fine pre-crosslinked rubber particles and mixing and dispersing them in a copolyelastomer.

In order to produce pre-crosslinked rubber, there is a method in which ordinary rubber is cross-linked with a vulcanizing agent and then pulverized to produce pre-crosslinked rubber particles. In this method, fine pre-crosslinked rubber particles are formed. Is difficult.

From the viewpoint of producing fine pre-crosslinked rubber particles and mixing and dispersing them in a copolyelastomer, JP-A-53-252 discloses that a polyester block copolymer is mixed with an ABS resin and / or an MBS resin. It is disclosed that a resin composition having excellent heat resistance, impact resistance, cold resistance and the like can be obtained. However, such an AB
Since the S resin and the MBS resin contain a glassy polymer component having a high glass transition temperature in the component thereof, it is possible to obtain a flexible thermoplastic elastomer excellent in tensile permanent elongation and compression set resistance, which is the object of the present invention. Is inappropriate.

Japanese Unexamined Patent Publication (Kokai) No. 63-142056 discloses a thermoplastic elastomer composition which is obtained by dispersing and mixing a polyester elastomer component with a rubber component containing 20% or more of a gel component and which has excellent flexibility and improved compression set. Has been done. However, the fluidity of the rubber component deteriorates and it is very difficult to finely disperse the rubber component in the polyelastomer component only by increasing the gel content defined by the content of the component insoluble in the good solvent. Becomes

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic elastomer composition which is flexible and has excellent tensile permanent elongation and compression strain resistance.

[0010]

According to the present invention, (A)
30 to 90% by weight of a thermoplastic copolyester elastomer or a thermoplastic copolyamide elastomer, and (B) a crosslinked rubber-like elastic core layer having a glass transition temperature of 25 ° C. or lower and an epoxy group or a carboxyl group in the molecule. Also provided is a thermoplastic elastomer composition comprising 70 to 10% by weight of a core-shell type rubber comprising a copolymer shell layer containing at least one functional group and having a glass transition temperature of 25 ° C. or lower.

The thermoplastic elastomer composition of the present invention will be described in detail below. The composition of the present invention comprises (A) a thermoplastic copolyester elastomer or a thermoplastic polyamide elastomer in an amount of 30 to 90% by weight, preferably 40.
To 80% by weight and (B) a glass transition temperature of 25 ° C. or less containing a crosslinked rubbery elastic core layer having a glass transition temperature of 25 ° C. or less and at least one functional group of an epoxy group or a carboxyl group in the molecule. Core shell type rubber comprising a copolymer shell layer 70 to 10% by weight, preferably 60
.About.20% by weight. If the ratio of (A) and (B) is out of the above range, and (A) is too small, the processability of the composition is lowered, and conversely, if (A) is too large, the effect of softening and rubber elasticity are imparted. The effect decreases.

The thermoplastic copolyester elastomer used in the present invention is a random or multiblock copolymer composed of repeating units of polyester and polyether, polyester, repeating units of (poly) lactone and polyether or repeating units of polyester and polyimide ether. Polyester, including copolyetherester elastomers, (poly) lactone modified copolyetherester elastomers and copolyetherimide ester elastomers.

Suitable thermoplastic copolyetherester elastomers and (poly) lactone-modified copolyetherester elastomers can be prepared by the conventional esterification / polycondensation method from (i) at least one diol and (ii) at least one diol. It is prepared from at least one dicarboxylic acid, (iii) at least one long-chain ether glycol and optionally (iv) at least one lactone or polylactone.

The diols (i) used in the preparation of the copolyetherester elastomers and their (poly) lactone-modified products include saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds. These diols preferably have a low molecular weight, i.e. about 300 or less. Specific examples of the aliphatic and alicyclic diols include ethylene glycol, propanediol, butanediol, pentanediol, 2-methylpropanediol, 2,2-dimethylpropanediol, hexanediol, decanediol and 2-octylundecanediol. , 1,2-, 1,
3- and 1,4-dihydroxycyclohexane, 1,
Mention may be made of diols having 2 to 15 carbon atoms, such as 2-, 1,3- and 1,4-cyclohexanedimethanol, butynediol, hexenediol. Particularly preferred diols are 1,4-butanediol and mixtures of 1,4-butanediol with hexanediol or butynediol. Specific examples of the aromatic diol include resorcinol, hydroquinone, and 1,5-
Mention may be made of diols having 6 to 19 carbon atoms such as dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis (p-hydroxyphenyl) methane and 2,2-bis (p-hydroxyphenyl) propane.

Particularly preferred diols are saturated aliphatic diols having 2 to 8 carbon atoms and mixtures of such saturated aliphatic diols, as well as mixtures of such saturated aliphatic and unsaturated diols. . If two or more diols are used, it is preferred that the same diol accounts for at least about 60 mol%, especially at least 80 mol%, based on the total amount of diols. The most preferred diol mixture is one in which 1,4-butanediol is the majority.

Suitable dicarboxylic acids (ii) for use in preparing the copolyetherester elastomers and their (poly) lactone-modified products include aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids. These dicarboxylic acids are preferably low molecular weight, i.e. having a molecular weight of about 350 or less, but higher molecular weight ones, especially dimer acids, can also be used.

Typical examples of the aliphatic and alicyclic dicarboxylic acids are sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4.
-Cyclohexanedicarboxylic acid, adipic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, allylmalonic acid, 4-cyclohexene-1,2-
Dicarboxylic acid, 2-ethylsuberic acid, tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-
1,5-naphthalenedicarboxylic acid, 4,4′-bicyclohexyldicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, 4,4-methylenebis (cyclohexanecarboxylic acid), 3,4-furandicarboxylic acid, and 1, 1-Cyclobutanedicarboxylic acid, as well as these dimer acids are mentioned. Among these, cyclohexanedicarboxylic acid, sebacic acid, glutaric acid and adipic acid are preferable.

Typical examples of the aromatic dicarboxylic acid include terephthalic acid, phthalic acid, isophthalic acid, beebenzoic acid,
Substituted dicarboxy compounds having two benzene nuclei such as bis (p-carboxyphenyl) methane, oxybis (benzoic acid) and ethylene-1,2-bis (p-oxybenzoic acid), 1,5-naphthalenedicarboxylic acid,
2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid,
And these halo and alkyl having 1 to 12 carbons,
It includes alkoxy and aryl group substituted derivatives.
As long as the achievement of the object of the invention is not hindered, other aromatic carboxylic acids such as p- (β-
A hydroxy acid such as hydroxyethoxy) benzoic acid can be used in combination.

Among the dicarboxylic acids used in the production of the copolyetherester elastomer and its (poly) lactone-modified products, among aromatic dicarboxylic acids and mixtures of two or more aromatic dicarboxylic acids, and aromatic dicarboxylic acids and fats. Mixtures with group and / or cycloaliphatic dicarboxylic acids are preferred, with aromatic dicarboxylic acids alone being particularly preferred. Among the aromatic dicarboxylic acids, aromatic dicarboxylic acids having 8 to 16 carbon atoms, especially benzenedicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and dimethyl esters thereof are preferable, and terephthalic acid is preferable. Dimethyl is the best. When using a mixture of dicarboxylic acids or their esters,
It is preferred that at least about 60 mol%, especially at least about 80 mol%, of the same dicarboxylic acid, based on the total amount of dicarboxylic acid. Especially, it is best that dimethyl terephthalate accounts for about 60 mol% or more of the dicarboxylic acid mixture.

The long-chain ether glycol (iii) used in the production of the thermoplastic copolyetherester elastomer and its (poly) lactone-modified product is preferably about 400.
Are poly (oxyalkylene) glycols and copoly (oxyalkylene) glycols having a molecular weight of about 12,000. Suitable poly (oxyalkylene) units are derived from long chain ether glycols having a molecular weight of about 900 to about 4,000 and having a carbon to oxygen ratio of about 1.8 to about 4.3 excluding side chains. To be done.

Representative examples of suitable poly (oxyalkylene) glycols are poly (ethylene ether) glycol, poly (propylene ether) glycol, poly (tetramethylene ether) glycol, ethylene oxide end-capped poly (propylene ether) glycol and a majority amount. Is a random or block copolymer of ethylene oxide and propylene oxide including copoly (propylene ether-ethylene ether) glycol having a poly (ethylene ether) skeleton, and tetrahydrofuran, and a small amount, for example, ethylene oxide, propylene oxide or methyltetrahydrofuran. Second
Random or block copolymers with the above monomers (used in proportions not exceeding about 4.3 carbon to oxygen). Formaldehyde, for example 1,4-
Polyformal glycols prepared by reacting diols such as butanediol and 1,5-pentanediol are also useful. Particularly preferred poly (oxyalkylene) glycols are poly (propylene ether) glycols, poly (tetramethylene ether) glycols and copoly (propylene ether-ethylene ether) glycols having a majority of polyethylene ether) skeleton.

If desired, one or more lactones or polylactones (iv) may be added to these copolyetheresters. This type of (poly) lactone-modified copolyetherester elastomer is disclosed in U.S. Pat. No. 4,569,973.

Suitable lactones (i) for use in the present invention
As v), ε-caprolactone is particularly preferable,
It is also possible to use substituted lactones which are substituted in the α, β, γ, δ or ε position with a lower alkyl group such as a methyl group or an ethyl group. Further, as the block unit of the copolyether ester used in the present invention, a homopolymer or a copolymer of a monomer thereof and another copolymerizable monomer and a polylactone including a hydroxy-terminated polylactone can be used.

In general, suitable copolyetherester elastomers and their (poly) lactone modifications are the amount of (iii) the long chain ether glycol component or (iii) in the copolyetherester or (poly) lactone modifications. The total amount of the long chain ether glycol component and the (iv) lactone component is about 5 to about 80% by weight. A more preferred composition is one in which the amount of (iii) long chain ether glycol component or the total amount of said (iii) component and (iv) lactone component is from about 10 to about 50% by weight.

The polyetherimide ester elastomer used in the present invention should be prepared from one or more diols, one or more dicarboxylic acids and one or more high molecular weight polyoxyalkylene diimide diacids. You can The manufacture of such polyetherimide ester elastomers is described in US Pat. No. 4,556,705.

The polyetherimide ester elastomers used in the present invention may be prepared by conventional methods for preparing polyesters, such as by esterification and condensation reactions to produce random or block copolymers. You can Thus, polyetherimide esters can generally be characterized as the reaction product of diols and acids.

Preferred polyetherimide ester elastomers used in the present invention are (i) one or more kinds of aliphatic or cycloaliphatic diols having 2 to 15 carbon atoms, (ii) one or more kinds of aliphatic diols. , An alicyclic or aromatic dicarboxylic acid or an ester derivative thereof, and (iii) one or more polyoxyalkylenediimidic diacids. The amount of polyoxyalkylenediimidic acid used generally depends on the desired properties of the resulting polyetherimide ester.
Generally, the weight ratio of polyoxyalkylene diimidodiacid (iii) to dicarboxylic acid (ii) is in the range of about 0.25 to about 2.0, preferably about 0.4 to about 1.4.

The diols (i) used in the preparation of the above polyetherimide esters include saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds. These diols have a low molecular weight,
That is, those having a molecular weight of about 250 or less are preferable.

Particularly preferred diols are saturated aliphatic diols, mixtures thereof and mixtures of one or more saturated aliphatic diols with one or more unsaturated aliphatic diols, provided that each diol is 2-8. It has 4 carbon atoms). When using more than one diol, at least about 60 based on total diol content.
It is preferred that mol%, more preferably at least 80 mol%, are the same diol. A particularly preferred diol is one having 1,4-butanediol as a main component, and the most preferred diol is 1,4-butanediol alone.

The dicarboxylic acid (ii) used in the production of the above polyetherimide ester is selected from aliphatic, alicyclic and aromatic dicarboxylic acids and their ester derivatives. Preferred dicarboxylic acids are those having a molecular weight lower than about 300, or those having 4 to 18 carbon atoms. However, higher molecular weight dicarboxylic acids,
In particular, dimer acid can also be used.

Among the aliphatic, alicyclic and aromatic dicarboxylic acids used for the production of the polyetherimide ester, aromatic dicarboxylic acids and mixtures of two or more aromatic dicarboxylic acids, as well as aromatic dicarboxylic acids and aliphatic and / Or a mixture with an alicyclic dicarboxylic acid is preferred, and the aromatic dicarboxylic acid alone is particularly preferred. Among the aromatic dicarboxylic acids, aromatic dicarboxylic acids having 8 to 16 carbon atoms, especially benzenedicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and dimethyl esters thereof are preferable, and terephthalic acid is preferable. Dimethyl is the best.

The polyoxyalkylenediimidic diacid (iii) used in the preparation of the polyetherimide ester is a high molecular weight diacid having an average molecular weight of greater than about 700, preferably greater than about 900. These diacids are composed of two adjacent carboxyl groups or acid anhydride groups, as well as another carboxyl group which must be esterifiable and preferably not imidizable. It is produced by imidizing one or more tricarboxylic acid compounds containing a) with a high molecular weight polyoxyalkylenediamine.

Generally, the polyoxyalkylenediimidic diacids useful in the production of polyetherimide esters are represented by the formula:

Embedded image

(In the formula, each R is a trivalent organic group, preferably an aliphatic, alicyclic or aromatic trivalent organic group having 2 to 20 carbon atoms, and each R may be the same or different. Of course, each R'is hydrogen or a monovalent organic group, preferably a monovalent organic group selected from an aliphatic group and an alicyclic group having 1 to 8 carbon atoms and an aromatic group having 6 to 12 carbon atoms, For example, a phenyl group, most preferably R'is hydrogen, each R'may be the same or different, and G is from about 600 to about 12,
Removal of hydroxy groups at both ends (or as close to the ends as possible) of a long chain ether glycol having an average molecular weight of 000, preferably about 900 to about 4,000 and a carbon / oxygen ratio of about 1.8 to about 4.3. It is a group that remains afterwards. )

The polyoxyalkylenediamine used to produce the polyoxyalkylenediimidic acid is produced from long chain ether glycol. Representative long chain ether glycols are poly (ethylene ether) glycols, poly (propylene ether) glycols, poly (tetramethylene ether) glycols, random or block copolymers of polyethylene oxide and propylene oxide, such as propylene oxide terminated poly (ethylene Ether) glycol, and tetrahydrofuran (used at a carbon / oxygen molar ratio in the glycol not exceeding about 4.3) and a small amount of a second monomer such as methyltetrahydrofuran in a random or block copolymer. Includes polymers. Particularly preferred poly (alkylene ether) glycols are poly (propylene ether) glycols and poly (propylene ether) glycols or propylene oxide endcapped poly (ethylene ether) glycols.

Generally, useful polyoxyalkylene diamines are from about 500 to about 12,000, preferably about 900.
Has an average molecular weight of about 4,000.

The tricarboxylic acid compound used to prepare the polyoxyalkylenediimidic acid comprises two adjacent imide-forming moieties in place of almost any carboxylic acid anhydride or acid anhydride group containing an additional additional carboxyl group. It can be the corresponding acid containing a carboxyl group. These acids may be used alone or as a mixture. The additional additional carboxyl group must be esterifiable and is preferably substantially imidizable.

The tricarboxylic acid compound is represented by the following formula.

Embedded image

(Wherein each R is a trivalent organic group, preferably an aliphatic, alicyclic or aromatic trivalent organic group having 2 to 20 carbon atoms, and each R may be the same or different. Of course, each R'is hydrogen or a monovalent organic group, preferably a monovalent organic group selected from an aliphatic group and an alicyclic group having 1 to 8 carbon atoms and an aromatic group having 6 to 12 carbon atoms, For example, a phenyl group, most preferably R'is hydrogen, each R'may be the same or different from each other, and the most preferred tricarboxylic acid compound is trimellitic anhydride.

The proportion of each component used for producing the polyetherimide ester is not particularly limited, but the diol (i)
Is preferably used in at least a molar equivalent, more preferably in molar excess, most preferably at least 150%, based on the total number of moles of dicarboxylic acid (ii) and polyoxyalkylenediimidic diacid (iii). Acid component [(ii) +
The use of a molar excess of diol with respect to (iii)] compensates for the loss of diol that occurs during esterification / condensation and gives the best yield.

The ratio of the dicarboxylic acid (ii) to the polyoxyalkylenediimidic diacid (iii) is not particularly limited either, but the (ii) / (iii) weight ratio is preferably about 0.25.
To about 2, more preferably about 0.4 to about 1.4. A particularly preferred ratio of the two is determined depending on the type of polyoxyalkylenediimidic diacid used and the desired physical and chemical properties of the resulting polyetherimide ester. Generally, the lower the weight ratio of polyoxyalkylenediimidic diacid (iii) / dicarboxylic acid (ii), the more excellent the strength, crystallinity and heat deflection of the resulting polymer. Conversely, the higher the (iii) / (ii) weight ratio, the better the flexibility, tensile strain and low temperature impact resistance of the resulting polymer.

Preferred polyetherimide esters for use in the present invention are dimethyl terephthalates, which may optionally contain up to 40 mol% of other dicarboxylic acids, optionally up to 40 mol% of other saturated or unsaturated fatty acids or fats. Made from 1,4-butanediol, which may include a cyclic diol, and polyoxyalkylenediamine having a molecular weight of about 600 to about 12,000, preferably about 900 to about 4,000, and trimellitic anhydride. It consists of the reaction product of polyoxyalkylenediimidic acid. The most preferred polyetherimide ester is obtained by using only 1,4-butanediol as the diol and only dimethyl terephthalate as the dicarboxylic acid in the reaction product obtained as described above.

The thermoplastic copolyamide elastomer used in the present invention includes a copolyesteramide elastomer which is a random or multiblock copolymer composed of repeating units of polyester and polyamide, and a random composition which is composed of repeating units of polyetherester and polyamide. Alternatively, it is roughly classified into a copolyether ester amide elastomer which is a multi-block copolymer.

The copolyester amide elastomer used in the present invention comprises (1) (a) an aminocarboxylic acid having 6 to 12 carbon atoms, (b) a lactam having 6 to 12 carbon atoms, and (c) 4 to 12 carbon atoms. Dicarboxylic acid and 4 to 12 carbon atoms
At least one polyamide-forming compound selected from nylon salts consisting of diamine and (2) carbon number of 4 to 54
It is obtained by reacting the dicarboxylic acid of (3) with polycaprolactone polyol (3).

Examples of the aminocarboxylic acid having 6 to 12 carbon atoms include 6-aminocaproic acid, 7-aminocaprylic acid, 8-aminocapric acid, ω-aminoenanthic acid and ω.
-Aminopelargonic acid, 11-aminoundecanoic acid, 1
2-aminododecanoic acid and the like can be mentioned, with 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid being particularly preferred. Examples of the lactam having 6 to 12 carbon atoms include caprolactam, enantolactam, capryllactam, and lauryllactam, with caprolactam and lauryllactam being particularly preferable. Examples of the nylon salt composed of a dicarboxylic acid having 4 to 12 carbon atoms and a diamine having 4 to 12 carbon atoms include adipic acid-hexamethylenediamine salt, sebacic acid-hexamethylenediamine salt, isophthalic acid-hexamethylenediamine salt, terephthalic acid- Examples include trimethylhexamethylenediamine salt.

Examples of the dicarboxylic acid having 4 to 54 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and diphenyl-4,4'-dicarboxylic acid. Acids, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,
Alicyclic dicarboxylic acids such as 4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanoic acid, and dimer acids thereof. Particularly preferred are terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dodecanoic acid, and dimer acids thereof.

The polycaprolactone polyol used together with the polyamide-forming compound and the dicarboxylic acid is preferably a polycaprolactone polyol having an average molecular weight of 200 to 10,000. If the molecular weight of the polycaprolactone polyol is greater than 10,000, the drawbacks of the polycaprolactone polyol are exposed. One preferable polycaprolactone polyol is polycaprolactone diol 7 having an average molecular weight of 200 to 10,000.
0-99.9% by weight and average molecular weight 200-10,000
And 0.1 to 30% by weight of polycaprolactone polyol having 3 or more functional groups. If the proportion of polycaprolactone polyol having 3 or more functional groups is less than 0.1% by weight, the effect will not be exhibited, and 3
If it exceeds 0% by weight, gelation tends to occur during production.

The above copolyesteramide elastomers are prepared by the reaction of an initiator, ε-caprolactone or 6-oxycaproic acid, a polyamide-forming compound and a dicarboxylic acid. The following method is mentioned as the manufacturing method. (A) A method of producing a polycaprolactone diol by ring-opening addition of ε-caprolactone to an initiator, followed by polycondensation reaction with the polycaprolactone diol, a polyamide-forming compound and a dicarboxylic acid. (B) A method in which a polyamide-forming compound is reacted with a dicarboxylic acid to form a dicarboxylic acid polyamide, and the polycarboxylic acid polyamide is produced by a polycondensation reaction with the polycaprolactone diol (A). (C) A method for producing by a ring-opening-polycondensation reaction of the dicarboxylic acid polyamide of (B) above with an initiator and ε-caprolactone. (D) A method of producing by a ring-opening-polycondensation reaction with an initiator, ε-caprolactone, a polyamide-forming compound and a dicarboxylic acid. When a polycaprolactone polyol mixture is used, a polyol mixture may be used instead of the diol in the above production method.

Examples of the initiator include the general formula HO.R.OH.
The diol represented by However, R is an aromatic hydrocarbon group having 1 to 2 aromatic rings, an alicyclic hydrocarbon group having 4 to 37 carbon atoms, a saturated or unsaturated aliphatic group having 1 to 30 carbon atoms, Average molecular weight 200 to 6,0
00 polyester polyol residue or average molecular weight 2
It is a polyalkylene glycol residue of 00 to 6,000.

The copolyether ester amide elastomer used in the present invention is synthesized by a condensation reaction between a polyether having a hydroxyl group at the chain end and a polyamide.
Examples of the polyether having a hydroxyl group at the chain end include a chain or branched polyoxyalkylene glycol, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol or a mixture thereof, or a copolyether derived from these compounds. Is. The average molecular weight of the above polyether is generally 200 to 6,000, preferably 400 to
It is 3,000. The weight ratio of polyoxyalkylene glycol based on the weight of all components is usually 5 to 85%, preferably 10 to 50%.

Polyamides used in the synthesis of copolyether ester amide elastomers include lactams or amino acids whose hydrocarbon chain has 4 to 14 carbon atoms, for example caprolactam, enantolactam, dodecaractam, undecanolactam, dodecanolactam, 11 Starting from -amino-undecanoic acid or 12-aminododecanoic acid, condensation products of dicarboxylic acids and diamines, such as hexamethylenediamine and adipic acid, azelaic acid, sebacic acid and 1,12-dodecanedioic acid Nylon 6-6, 6-9, 6-, which is a condensation product of the above and a condensation product of nonamethylenediamine and adipic acid
10, 6-12 and 9-6.

The diacid used as a chain limiter in the polyamide synthesis reaction likewise allows the production of a carboxylic acid-terminated polyamide, but the diacid is
Dicarboxylic acids, preferably aliphatic dicarboxylic acids having 4 to 20 carbon atoms, such as succinic acid, adipic acid, suberic acid,
Mention may be made of azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid. Alicyclic or aromatic diacids can also be used. These diacids are in excess of those required to obtain a polyamide having the desired average molecular weight according to known calculation methods currently used in the field of polycondensation reactions. The average molecular weight of the dicarboxylic acid polyamide is usually 300 to 15,000, preferably 800 to
It is 5,000.

The polycondensation reaction for producing the copolyether ester amide elastomer is carried out under stirring in the presence of a catalyst under a high vacuum of about 0.05 to 5 mmHg at a temperature higher than the melting point of the components used. This temperature is
The reaction components are selected so that they remain fluid. That is, generally 100 to 400 ° C., preferably 200 to 3
It is 00 ° C. The reaction time depends on the polyoxyalkylene glycol, but it is generally in the range of 10 minutes to 10 hours, preferably 1 to 7 hours. The reaction time must be long enough to obtain the final viscosity needed to obtain a product with the desired properties required for moldable and / or extrudable plastic materials. To obtain the desired product, the carboxylic acid groups and the hydroxyl groups must be substantially equimolar so that the polycondensation reaction takes place under optimum conditions.

The core-shell type rubber (B) which is another component used in the thermoplastic elastomer composition of the present invention is a crosslinked rubber-like elastic core layer having a glass transition temperature of 25 ° C. or lower, preferably 0 ° C. or lower. And a copolymer shell layer. If the core layer and / or the shell layer deviates from the above range, the softening effect is significantly reduced.

The core-shell type rubber (B) which is another component used in the thermoplastic elastomer composition of the present invention includes natural rubber, polyisoprene rubber and styrene-
Butadiene rubber, styrene-butadiene block copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber and other diene rubbers, or ethylene-propylene rubber, ethylene-propylene terpolymer rubber, acrylic rubber, fluorine rubber and other non-rubber Examples thereof include hydrogenated rubbers such as diene rubber or hydrogenated acrylonitrile-butadiene rubber and hydrogenated styrene-butadiene block copolymer rubber. Both the core layer and the shell layer can be independently selected from these rubbers, but the polymer composition must be selected so that the glass transition temperature is 25 ° C. or lower. Among these, a rubber containing a conjugated diene as a main component such as polybutadiene, acrylonitrile-butadiene rubber and chloroprene rubber, and an acrylic rubber containing an alkyl methacrylate or an alkyl acrylate as a main component are preferable.

The crosslinked rubber-like elastic core layer of the present invention is a polymer in which the core layers are crosslinked with each other in a network, and the gel amount represented by the amount of components insoluble in a good solvent is As an index, the gel amount is 70% by weight or more, preferably 80% by weight or more. If the amount of gel in the core layer is too small, the compression set is large and the rubber elasticity imparting effect is reduced.

The rubber of the core layer is preferably composed mainly of a conjugated diene or an alkyl (meth) acrylate or an alkoxyalkyl (meth) acrylate, and if necessary, other ethylenically unsaturated copolymerizable with them. It is formed from a monomer and a crosslinkable monomer. The monomer composition used for forming the core layer rubber is based on the total weight of the monomers (i)
50 to 100% by weight of a conjugated diene or alkyl (meth) acrylate or alkoxyalkyl (meth) acrylate, 50 to 0% by weight of another copolymerizable ethylenically unsaturated monomer, and (iii) crosslinkability When a monomer is used, it comprises 0.01 to 10% by weight of a crosslinkable monomer. Examples of the conjugated diene include 1,3-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene.

As the (meth) acrylic acid alkyl ester, those having an alkyl group having 1 to 18 carbon atoms are used. Specific examples of such (meth) acrylic acid alkyl ester include methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-methylpentyl (meth) acrylate, n-octyl (meth) acrylate, 2-
Examples thereof include ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, and n-octadecyl (meth) acrylate. Among them, ethyl (meth) acrylate, n-propyl (meth) acrylate, Preferred are n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-octyl (meth) acrylate.

As the (meth) acrylic acid alkoxy-substituted alkyl ester, those having an alkyl group having 1 to 18 carbon atoms having an alkoxy substituent having 1 to 18 carbon atoms are used. Specific examples of the acid alkyl ester include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, 2- (n-butoxy) ethyl (meth ) Acrylate, 3-methoxypropyl (meth) acrylate, 3
-Ethoxypropyl (meth) acrylate, 2- (n-
Propoxy) propyl (meth) acrylate, 2- (n
-Butoxy) propyl (meth) acrylate and the like.

If necessary, a conjugated diene or (meth)
Examples of the monomer copolymerizable with the acrylic acid alkyl ester or the (meth) acrylic acid alkoxy-substituted alkyl ester include 2-cyanoethyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, and 4-cyanobutyl (meth) acrylate. Amino-substituted alkyl (meth) such as cyano-substituted alkyl (meth) acrylate and diethylaminoethyl (meth) acrylate
Acrylate, fluorine-containing (meth) acrylate such as 1,1,1-trifluoroethyl (meth) acrylate, hydroxyl group-substituted alkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, alkyl such as methyl vinyl ketone Vinyl or allyl ether such as vinyl ketone, vinyl ethyl ether and allyl methyl ether, vinyl aromatic compound such as styrene, α-methyl styrene, chlorostyrene and vinyl toluene,
Vinyl nitriles such as acrylonitrile and methacrylonitrile, acrylamide, methacrylamide, N-
Vinyl amides such as methylol acrylamide and ethylene, propylene, vinyl acetate and the like can be mentioned.

Examples of the crosslinkable monomer include aromatic compounds such as divinylbenzene and 1,3,5-trivinylbenzene, ester compounds such as diallyl phthalate and diallyl fumarate, trimethylolpropane trimethacrylate and ethylene glycol. Dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, allyl methacrylate, vinyl methacrylate, etc. The monomer which it has is mentioned.

The copolymer shell layer of the present invention is an essentially fluid component, and when the copolyelastomer and the core-shell type rubber are melt-mixed, the rubber component is fluidized and dispersed in the copolyelastomer matrix. It has the effect of making it easier. That is, the core-shell type rubber of the present invention has a copolymer shell layer containing at least one functional group selected from an epoxy group and a carboxyl group, and when these functional groups are melt-mixed, the rubber is It has the effect of facilitating fine dispersion of the components in the copolyelastomer matrix. This is presumed to be because these functional groups react with the copolyelastomer molecule to form a graft body to enhance the compatibility of the interface between the rubber component and the copolyelastomer component.

The preferred rubber forming the shell layer is based on a conjugated diene or alkyl (meth) acrylate or alkoxy substituted alkyl (meth) acrylate as the main component,
It is formed from an epoxy group- or carboxyl group-containing ethylenically unsaturated monomer copolymerizable therewith, and optionally another ethylenically unsaturated monomer copolymerizable therewith. The monomer composition used to form the shell layer rubber is
(I) Conjugated diene or alkyl (meth) acrylate or alkoxy-substituted alkyl (meth) acrylate 50
To 99.9% by weight, (ii) epoxy group- or carboxyl group-containing ethylenically unsaturated monomer 0.1 to 15% by weight, and (iii) other copolymerizable ethylenically unsaturated monomer 0 to 49 .9% by weight.

As the conjugated diene and the alkyl (meth) acrylate and the alkoxy-substituted alkyl (meth) acrylate used for forming the shell layer rubber, the same monomers as those used for forming the core layer rubber are used. be able to

The epoxy group- or carboxyl group-containing ethylenically unsaturated monomer is a copolymerizable ethylenically unsaturated monomer containing at least one functional group selected from the epoxy group and the carboxyl group. if there is,
Although not particularly limited, preferred epoxy group-containing ethylenically unsaturated monomers include allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and the compounds shown below.
Among these, glycidyl (meth) acrylate and allyl glycidyl ether are particularly preferable.

3,4-Epoxyhexahydrobenzyl (meth) acrylate 4-glycidyloxy-3,5-dimethylbenzyl (meth) acrylate 2- (4'-glycidyloxyphenyl) -2- [4 '
-(Meth) acryloxyethyloxyphenyl] propane 2- (meth) acryloyloxyethyl succinic acid glycidyl ester 2- (meth) acryloyloxyethyl phthalic acid glycidyl ester 2- (meth) acryloyloxyethyl hexahydrophthalic acid glycidyl ester 2 -(Meth) acryloyloxyethyl terephthalic acid glycidyl ester 2- (meth) acryloyloxyethyl hexahydroterephthalic acid glycidyl ester 3,4-epoxyhexahydrobenzyl (meth) acrylamide 4-glycidyloxy-3,5-dimethylbenzyl (meth ) Acrylamide

Preferred carboxyl group-containing ethylenically unsaturated monomers used for forming the shell layer rubber include acrylic acid, methacrylic acid, crotonic acid, 2-pentynoic acid, maleic acid, fumaric acid and itaconic acid. And mono- and dicarboxylic acids of. Furthermore, an acid anhydride group of dicarboxylic acid or a monoalkyl ester or monoamide represented by the following general formula can also be used. ^{_{CH 2 = C (R 1)}} CO-O · R 2 · O · CO · R 3 · CO
OH (wherein R ¹ is hydrogen or a methyl group, R ² is a carbon number of 2 to 6)
R ³ represents a phenylene group, a cyclohexylene group, an alkylene group having 2 to 6 carbon atoms, or a divalent unsaturated hydrocarbon group. )

Specific examples of such compounds include CH ₂ ═C (CH ₃ ) CO—O.CH ₂ CH ₂ .O—CO—
_{CH 2 CH 2 -COOH CH 2 =} C (CH 3) CO · O · CH 2 CH 2 · O-CO-
_{CH = CH · COOH CH 2 =} C (CH 3) CO · O · CH 2 CH 2 · O-CO-
ph-COOH (ph = _{phenylene) CH 2 = C (CH 3} ) CO · O · CH 2 CH 2 · O-CO-
ch-COOH (ch = cyclohexene) and the like, and further succinic acid mono- (meth) acrylooxy ester, maleic acid mono- (meth) acrylooxy ester, phthalic acid mono- (meth) acrylooxy ester, hexa. Hydrophthalic acid (meth) acrylooxy ester, succinic acid mono- (meth) acrylooxypropyl ester, maleic acid mono- (meth) acrylooxypropyl ester, phthalic acid mono- (meth) acrylooxypropyl ester, Hexahydrophthalic acid mono-
Examples thereof include (meth) acrylooxypropyl ester, adipic acid mono (meth) acrylooxyethyl ester, and malonic acid mono (meth) acrylooxyethyl ester. Among these vinyl monomers containing a carboxyl group, acrylic acid and methacrylic acid are preferred.

If necessary, a conjugated diene or (meth)
As the monomer to be copolymerized with the acrylic acid alkyl ester or the (meth) acrylic acid alkoxy-substituted alkyl ester, the epoxy group-containing ethylenically unsaturated monomer and / or the dicarboxyl group-containing ethylenically unsaturated monomer, a core is used. The same ethylenically unsaturated monomer as described above, which is used as an optional monomer component for forming the layer rubber, is used.

Particularly, as the ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a functional group other than an epoxy group or a carboxyl group, for example, an amino group-containing ethylenically unsaturated monomer or a hydroxyl group-containing ethylene is used. It is also possible to introduce a functional group such as an amino group or a hydroxyl group into the shell layer rubber by copolymerizing a polyunsaturated monomer.

As the amino group-containing ethylenically unsaturated monomer, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dibutylaminoethyl methacrylate, dibutylaminopropyl methacrylate,
Examples include (meth) acrylic acid ester-based monomers such as diethylaminobutyl methacrylate, dihexylaminoethyl methacrylate, dioctylaminoethyl methacrylate, and amino group-containing ethylenically unsaturated monomers such as 2-vinylpyridine and 4-vinylpyridine. . Among these amino group-containing ethylenically unsaturated monomers, diethylaminoethyl methacrylate, 2-vinylpyridine, 4
-Vinylpyridine is preferred.

Examples of the hydroxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid ester monomers such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.

Examples of the method for producing the core-shell type rubber of the present invention include the following two methods. (1) While kneading the rubbers of I and II, add a vulcanizing agent that crosslinks only the rubber of I to make a structure in which the crosslinked rubber of I is dispersed in the rubber of II. Layer II is the shell layer. (2) After a crosslinked rubber-like elastic core latex is prepared by multistage addition emulsion polymerization, a core-shell type latex having a copolymer shell layer formed around the core layer is prepared. Then, the latex is coagulated and dried to obtain a core-shell type rubber. The method (2) is more preferable from the viewpoint of production difficulty,
The method is not limited as long as it meets the purpose of the present invention.

The core-shell type rubber of the present invention is preferably 10 to 80% by weight, more preferably 20 to 70% by weight.
And a shell layer of preferably 20 to 90% by weight, more preferably 30 to 80% by weight. If it deviates from the above and the core layer becomes too small, the rubber elasticity imparting effect decreases,
On the other hand, if the amount is too large, the fluidity of the core-shell type rubber decreases, and it becomes difficult to finely disperse the rubber.

The thermoplastic elastomer composition of the present invention is prepared by kneading a thermoplastic copolyester elastomer or thermoplastic copolyamide elastomer and the above core-shell type rubber at a softening temperature or higher to a melting temperature or lower. The kneading is generally 100 to 280 ° C., preferably 140 to 25
Perform for about 1 to 30 minutes at 0 ° C. The kneading for preparing the composition of the present invention is preferably carried out under a sufficient shearing force, and as a suitable kneading device, a single-screw extruder, a twin-screw extruder, a Buss type co-kneader, a Banbury mixer, a furrel (Farrell) type continuous mixer, K
CK type mixer and the like can be mentioned. The rubber component and the elastomer component may be added to the kneading device by blending the rubber component and the elastomer component in advance, or measuring each component separately and adding them at the same time, or adding one or both components to the kneading device. May be added in portions or added sequentially.

Thus, the thermoplastic copolyester elastomer or the thermoplastic copolyamide elastomer is melt-mixed together with the core-shell type rubber, and the core-shell type rubber component is reacted with the functional group of the shell layer by a compound capable of crosslinking the rubber component. It is dynamically crosslinked and dispersed in a matrix of thermoplastic copolyester or thermoplastic copolyamide elastomer.

Various additives can be added to the composition of the present invention. Examples of such additives include calcium carbonate, calcium silicate, clay, kaolin,
Fillers and reinforcing agents such as talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite and carbon fiber;
Coloring agents such as carbon black, ultramarine blue, titanium oxide, zinc white, red iron oxide, dark blue, azo pigments, nitrone pigments, lake pigments, phthalocyanine pigments; mineral oil rubber softeners called process oils or extender oils,
Dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimellitic acid ester, dioctyl adipate, dioctyl azelate, dioctyl sebacate, epoxy fatty acid ester Plasticizers such as; and phenylenediamine-based,
Examples include isidazole-based and hindered phenol-based antioxidants. The additives may be blended in advance in the copolyester elastomer or copolyamide elastomer or the above core-shell type rubber, may be added while kneading these rubbers, or may be mixed in the composition after preparation.

[0078]

EXAMPLES The thermoplastic elastomer composition of the present invention will be specifically described below with reference to examples. In the following examples and comparative examples, unless otherwise specified, JIS
The measurement was performed according to K-6301. The resin materials, dynamic cross-linking agents and additives used are represented by abbreviations in each example, and the details are as follows. Copolyester elastomer COPE1: Hytrel 5557 made by Du Pont COPE2: Lomod XB0125 made by General Electric (GB) Copolyamide elastomer CAPA: Pebax 5533SA00 made by Ateochem

Dynamic Crosslinking Agent Crosslinking Agent 1: Butanetetracarboxylic Acid Crosslinking Agent 2: Bisphenol S Diglycidyl Ether Crosslinking Agent 3: Dicyandiamide Additive Antiaging Agent: Irganox 1010

Production of core-shell type rubber (1) Preparation of crosslinked rubber-like elastic core latex (C1) Using an autoclave with an internal volume of 13 liters, 65 parts of butadiene and 35 parts of acrylonitrile were exchanged with ion-exchanged water 2
In 00 parts, emulsifier, chelating agent, sodium sulfate,
Emulsion polymerization was carried out using ammonium persulfate and t-dodecyl mercaptan under the following conditions. Polymerization temperature 4
The reaction was carried out at 0 ° C. for 6 hours and then at 50 ° C. for 8 hours to obtain a core latex (C1) having a solid content concentration of 33.7%.
The polymerization conversion rate reached 98.9%. A part of the core latex was taken out, salted out and solidified with an aqueous magnesium sulfate solution, and vacuum dried at about 60 ° C. to obtain a core component rubber. 0.5 g of the obtained core component rubber was shredded, 100 ml of methyl ethyl ketone was added, and the mixture was allowed to stand at 25 ° C. for 24 hours. The insoluble matter was filtered with a 200 mesh wire mesh and then vacuum dried at about 60 ° C. to weigh the gel component. The gel amount was 95% by weight.

(2) Preparation of Crosslinked Rubbery Elastic Core Latex (C2) 98 parts of butyl acrylate and 2 parts of allyl methacrylate were placed in 200 parts of ion-exchanged water in a glass polymerization reactor having an internal volume of 2 liters. Then, emulsion polymerization was performed under the following conditions. A polymerization reactor was charged with 160 parts of ion-exchanged water and a chelating agent, and nitrogen gas was blown thereinto to remove dissolved oxygen. First, an emulsifier, a chelating agent and sodium sulfate are dissolved in ion-exchanged water, and the monomer 10 is stirred with stirring.
A monomer emulsion was prepared by adding 0 part and 0.03 part of PMHP. Next, SFS and FrostFe were dissolved in 10 parts of ion-exchanged water to prepare an active aqueous solution. After adding 10% by weight of the monomer emulsion to the polymerization reactor,
Paramenthane hydroperoxide (P
MHP) (0.005 parts) and 10% by weight of the active aqueous solution were added and reacted. After 1 hour, the remaining monomer emulsion was continuously added over 3 hours. The active aqueous solution was continuously added over 4 hours. After the addition was completed, the post-reaction was further continued for 3 hours to obtain a core latex (C2) having a solid component concentration of 33.5%. The polymerization temperature was changed at 10 to 15 ° C. The polymerization conversion rate was 98.5%. A part of the core latex (C2) was treated in the same manner as above, and the gel amount was measured and found to be 92% by weight.

(3) Core-shell type rubber (CS1-1)
In a glass polymerization reactor having an internal volume of 2 liters, 97 parts of butyl acrylate and 3 parts of glycidyl methacrylate were added to 200 parts of ion-exchanged water in the presence of 127.2 parts of the core latex (C1). The emulsion polymerization was carried out under the conditions of. In advance, 160 parts of ion-exchanged water, 130 parts of a chelating agent and 130 parts of core latex were charged in a polymerization reactor, and nitrogen gas was blown thereinto to remove dissolved oxygen. Next, an emulsifier, a chelating agent, and sodium sulfate were dissolved in ion-exchanged water, and 100 parts of the monomer, 0.03 part of PMHP and 0.12 part of t-dodecyl mercaptan were added with stirring to prepare a monomer emulsion. Also, ion-exchanged water SFS
And FrostFe were dissolved to prepare an active aqueous solution. After adding 10% by weight of the monomer emulsion to the polymerization reactor, 0.005 parts of PMHP and 10% by weight of the active aqueous solution were added and reacted with stirring. After 1 hour, the remaining monomer emulsion was continuously added over 3 hours.
The active aqueous solution was continuously added over 4 hours. After the addition was completed, the reaction was further continued for 3 hours to obtain a core-shell structured latex. The polymerization temperature was changed at 10 to 15 ° C.
The polymerization conversion rate was 97.8%. The core-shell structure latex was coagulated and dried in the same manner as described above to obtain a core-shell type rubber (CS1-1). The weight ratio of the core layer and the shell layer of CS1-1 is 3: 7. The gel amount of CS1-1 was less than 1% by weight. However, the filtered methyl ethyl ketone solution was cloudy, and it is presumed that a fairly fine gel-like substance was dispersed.

(4) Preparation of Copolymer of Shell Layer Portion Only the core latex was removed from the emulsion polymerization formulation of CS1-1, polymerization was carried out in the same manner, and coagulation drying was carried out as described above. The gel amount of the obtained copolymer is less than 1% by weight,
The filtered methyl ethyl ketone solution was transparent. From this, it is considered that when a core-shell type rubber such as CS1-1 is dissolved in a good solvent, the shell layer portion is dissolved and the core layer, which is a crosslinked body, is redispersed in a latex form.

(5) Core-shell type rubber (CS2-1)
In a glass polymerization reactor having an internal volume of 2 liters, 98 parts of butyl acrylate and 2 parts of glycidyl methacrylate were added to 200 parts of ion-exchanged water in the presence of 199.1 parts of core latex (C2) to prepare the following. Emulsion polymerization was performed under the conditions. In advance, 160 parts of ion-exchanged water, 200 parts of a chelating agent and core latex were charged in a polymerization reactor, and nitrogen gas was blown thereinto to remove dissolved oxygen. Next, an emulsifier, a chelating agent, and sodium sulfate were dissolved in ion-exchanged water, and 100 parts of the monomer, 0.03 part of PMHP and 0.12 part of t-dodecyl mercaptan were added with stirring to prepare a monomer emulsion. In addition, SF is added to ion-exchanged water.
An active aqueous solution was prepared by dissolving S and FrostFe.
After adding 10% by weight of the monomer emulsion to the polymerization reactor, 0.005 parts of PMHP and 10% by weight of the active aqueous solution were added and reacted with stirring. After 1 hour, the remaining monomer emulsion was continuously added over 3 hours.
The active aqueous solution was continuously added over 4 hours. After the addition was completed, post-reaction was further performed for 3 hours to obtain a core-shell structured latex. The polymerization temperature was changed at 10 to 15 ° C. The polymerization conversion rate was 98.3%. The core-shell structured latex was coagulated and dried in the same manner as above to obtain a core-shell type rubber (CS2-1). The amount of gel of CS2-1 is CS
It was the same as 1-1.

(6) Core-shell type rubber (CS1-2,
Preparation of CS2-2) The core-shell type rubbers CS1-2 and CS2-2 were prepared according to the above so that the charged composition and the core-shell ratio shown in Table 1 were obtained. In addition, the gel amount of the core part, T of the core part
g, Tg of the shell portion, and gel amount of the core-shell rubber are also shown in Table 1.

Preparation of Comparative Rubber (1) Core-shell type rubber (CS1-3, CS1-4,
CS3-1, CS4-1) Core-shell type rubber CS1-3, CS1-4, CS3-
1 and CS4-1 were prepared according to the above so that the charged composition and core shell ratio shown in Table 2 were obtained. Also,
Table 2 also shows the gel amount of the core portion, the Tg of the core portion, the Tg of the shell portion and the gel amount of the core-shell rubber. (2) Preparation of rubbers (R1, R2) R1 and R2, which are the general categories of rubber, were prepared according to the production method of C1 and C2 so that the charged compositions shown in Table 3 were obtained. Gel amount and Tg of each rubber
Is also shown in Table 3.

Examples 1 and 2 The thermoplastic elastomer compositions of the present invention were prepared as follows. That is, using a Toyo Seiki Co., Ltd. Labo Plastomill (internal volume of about 600 ml), first, the copolyelastomer was put into a mixer preheated to 230 ° C. and melted,
The rubber was added and mixed for 5 minutes, the cross-linking agent and the additives were added, and mixed for another 7 minutes. After the completion, the mixture was immediately taken out, formed into a sheet with a roll preheated to 180 ° C., and formed into a 1 mm thick sheet by a press preheated to 230 ° C., and subjected to a physical property evaluation test. The ratio of each material is shown in Table 4. In addition, Table 4 also shows the results of evaluating the physical properties of the obtained thermoplastic elastomer composition. Comparative Examples 1-6
Compared with, the thermoplastic elastomer has excellent tensile permanent elongation that exhibits rubber-like elastic behavior.

Comparative Examples 1 to 6 The compositions of Comparative Examples were prepared in the same manner as in Examples 1 and 2 and subjected to a physical property evaluation test. Table 4 shows the ratio of each material and the evaluation results of physical properties. In Comparative Examples 2 and 5, the dispersibility of the rubber component was poor, and there were many coarse rubber coarse dispersions that could be visually discerned, and the tensile elongation of the composition significantly decreased. Further, Comparative Example 4 is a composition containing a high Tg component in the core layer, but the hardness is remarkably higher than those of other compositions, and when a core-shell type rubber containing a high Tg component in the rubber component is used, The softening effect of the composition is significantly reduced.

Examples 3 to 7 The thermoplastic elastomer compositions of the present invention were prepared as follows. That is, a twin-screw extruder 2D25F (26 mmφ, L / D connected to a Labo Plastomill manufactured by Toyo Seiki Co., Ltd.
= 25), the barrel set temperature is 240 ° C., the rotation speed is 250 rpm, the extrusion rate is 3 kg / hr, and each material is shown in Table 5.
The mixture was mixed so as to have the ratio shown in. The composition is 2D25F
A T-shaped die having a width of 6 cm was connected to the head portion of the above, and the sheet was directly extruded into a sheet. The obtained sheet-shaped composition was directly subjected to a physical property evaluation test. The evaluation results are also shown in Table 5. Each of the compositions is a thermoplastic elastomer composition which is flexible and has excellent tensile set and compression set.
In particular, Examples 5 and 7 exhibited excellent tensile set and compression set despite the fact that no dynamic crosslinking agent was used.

[0090] Similar compositions of Comparative Examples 7-9 Comparative Examples 7-9 and Examples 3-7 were prepared such that the ratio of each material shown in Table 5, the property evaluation results are shown in Table 5 . The composition of Comparative Example 8, which does not use the dynamic crosslinking agent, has very poor tensile set and compression set. Although the dynamic crosslinking agents are used in Comparative Examples 7 and 9, it can be said that the effect of improving the tensile elongation and compression set is considerably small.

[0091]

FUNCTION AND EFFECTS OF THE INVENTION As described in the above examples, (A) the thermoplastic copolyester elastomer or thermoplastic copolyamide elastomer of the present invention and (B) the crosslinked rubber-like elasticity having a glass transition temperature of 25 ° C. or lower. A thermoplastic elastomer composition composed of a core-shell type rubber comprising a body core layer and a copolymer shell layer containing an epoxy group and / or a carboxyl group and having a glass transition temperature of 25 ° C. or lower, has a core-shell type rubber The shell layer has the effect of imparting fluidity to the rubber component and making it easily dispersed in the copolyelastomer matrix. It is presumed that this is because the epoxy or carboxyl functional group reacts with the copolyelastomer molecule to form a graft body to improve the compatibility of the interface between the rubber component and the elastomer component. Therefore, the thermoplastic elastomer composition of the present invention produces a vulcanized product which is flexible and has excellent tensile set and compression set.

(A) Thermoplastic Copolyester Elastomer or Thermoplastic Copolyamide Elastomer 3 of the Present Invention
0 to 90% by weight, and (B) glass transition temperature is 25 ° C.
Core-shell type comprising the following crosslinked rubber-like elastic core layer and a copolymer shell layer containing at least one functional group selected from epoxy groups and carboxyl groups in the molecule and having a glass transition temperature of 25 ° C. or lower The preferred embodiments of the thermoplastic elastomer composition comprising 70 to 10% by weight of rubber are summarized below.

(1) The thermoplastic elastomer composition comprises (A) 40 to 80% by weight of a thermoplastic copolyester elastomer or thermoplastic polyamide elastomer, and (B) 60 to 20% by weight of the above core-shell type rubber. (2) The glass transition temperature of the core layer and the shell layer of the core-shell type rubber is 0 ° C. or lower.

(3) The thermoplastic copolyester elastomer is at least one selected from copolyetherester elastomers, (poly) lactone-modified copolyester elastomers and copolyetherimide ester elastomers. (4) The thermoplastic polyamide elastomer is at least one selected from copolyether ester amide elastomer and copolyester amide elastomer. (5) The core-shell type rubber comprises a core layer of 10 to 80% by weight and a shell layer of 20 to 90% by weight.

(6) The gel amount of the core layer is 70% by weight or more,
It is more preferably 80% by weight or more. (7) The core layer is a crosslinked elastic core layer in which a conjugated diene or a (meth) acrylic acid alkyl ester or a (meth) acrylic acid alkoxyalkyl ester is crosslinked as a main component. (8) The core layer comprises (i) 50 to 99.99% by weight of conjugated diene or alkyl (meth) acrylate or alkoxy-substituted alkyl (meth) acrylate, and (ii) other copolymerizable ethylenically unsaturated monomer. It is composed of a crosslinked rubber-like elastic body formed from 49.99% to 0% by weight of the body and 0.01% to 10% by weight of the (iii) crosslinking monomer.

(9) The shell layer is a copolymer shell layer containing a conjugated diene or (meth) acrylic acid alkyl ester or (meth) acrylic acid alkoxyalkyl ester as a main component and having essentially fluidity. (10) The shell layer comprises (i) a conjugated diene or an alkyl (meth) acrylate or an alkoxy-substituted alkyl (meth) acrylate of 50 to 50
99.99% by weight, (ii) 0.1 to 15% by weight of an epoxy group- or carboxyl group-containing ethylenically unsaturated monomer, and (iii) another copolymerizable ethylenically unsaturated monomer of 0 to 49. It consists of a copolymer formed from 9% by weight. (11) The epoxy group-containing ethylenically unsaturated monomer of (10) above is at least one selected from glycidyl (meth) acrylate and allyl glycidyl ether. (12) The carboxyl group-containing ethylenically unsaturated monomer of (10) above is at least one selected from acrylic acid and methacrylic acid.

(13) The thermoplastic copolyester elastomer or the thermoplastic copolyamide elastomer is melt mixed with the core-shell type rubber, and the core-shell type rubber component is dispersed in the matrix of the thermoplastic copolyester or the thermoplastic copolyamide elastomer. . (14) The thermoplastic copolyester elastomer or the thermoplastic copolyamide elastomer is melt-mixed together with the core-shell type rubber, and the core-shell type rubber component is dynamically cross-linked by a compound capable of crosslinking the rubber component by reaction with the functional group of the shell layer. And are distributed in the matrix.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Kotsuji 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Corporation R & D Center

Claims (1)

[Claims] 1. (A) Thermoplastic copolyester elastomer or thermoplastic copolyamide elastomer 30 to 9
0% by weight, and (B) a glass transition temperature containing a crosslinked rubber-like elastic core layer having a glass transition temperature of 25 ° C. or lower and at least one functional group selected from an epoxy group and a carboxyl group in the molecule. A thermoplastic elastomer composition comprising 70 to 10% by weight of a core-shell type rubber comprising a copolymer shell layer having a temperature of 25 ° C. or less.