JPH10120910A - Thermoplastic elastomer composition - Google Patents

Abstract

[PROBLEMS] To provide non-adhesiveness, low friction, water and oil repellency, etc. of a molded article obtained from a thermoplastic elastomer while maintaining the moldability of the thermoplastic elastomer, particularly the melt flowability. I do. A fluorinated alkyl group-containing (meth) acrylate monomer (A) having a specific structure and a non-fluorinated (meth) acrylate in which the ester substituent is a linear or branched alkyl group having 10 to 30 carbon atoms. The present invention relates to a thermoplastic elastomer composition comprising a copolymer (I) and a thermoplastic elastomer (II), characterized by containing a (meth) acrylate monomer (B) as a copolymer component.

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 having a surface-modifying effect on the surface of a molded product such as water / oil repellency, low friction, and non-adhesion.

[0002]

2. Description of the Related Art Thermoplastic elastomers have been applied to a wide range of fields due to their excellent properties.

[0003] However, thermoplastic elastomers generally have the disadvantage of having high tackiness and poor surface slipperiness. In particular, low-hardness products are not only problematic in releasability during molding, but also have difficulties in handling, which limits their applications.

In order to remedy this drawback, it is common practice to add a lubricant having a higher alkyl group. However, a so-called bleeding phenomenon in which the lubricant migrates to the surface of the molded product and powder is deposited on the surface. Occurs, or adversely affects the moldability, so that the amount added is limited and sufficient effects cannot be obtained.

In order to improve the above-mentioned drawbacks, for example, with respect to polyurethane elastomers, Japanese Patent Application Laid-Open No. 3-40731 is disclosed.
Japanese Patent Application Laid-Open No. 2-63464 and Japanese Patent Application Laid-Open No.
No. 223011 proposes introducing a perfluoropolyether into the polyurethane main chain. Japanese Patent Application Laid-Open No. Hei 2-135210 discloses that a polysiloxane is introduced into a side chain.
JP-A-2-258821 and JP-A-2-2588
No. 22 proposes to introduce a polyfluoroalkyl group into a side chain.

However, in these methods, the physical properties of the elastomer, for example, strength, abrasion resistance and the like are reduced, and the effect of sufficiently improving the surface slip property is not obtained. Further, from the viewpoint of enhancing the surface function, there has not yet been invented any compound which can provide several kinds of performances such as water and oil repellency and low friction with only one kind of compound.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve such problems and to reduce the molding workability similar to or higher than the conventional one and to reduce the physical properties of general thermoplastic elastomer compositions. Another object of the present invention is to provide a thermoplastic elastomer composition having a non-adhesiveness, a low friction property, and a water and oil repellency, which have never been seen before, on the surface of the obtained molded article.

[0008]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and found that the (meth) acrylate monomer containing a fluorinated alkyl group and the ester substituent have 10 to 30 carbon atoms. Non-fluorine (meth) acrylate monomer (B) which is a linear or branched alkyl group
By adding a copolymer characterized by containing as a copolymer component to the thermoplastic elastomer, it is possible to reduce the resin flow start temperature when molding by a method such as extrusion molding, injection molding, and It has been found that not only is it possible to remarkably reduce the tackiness of the surface of a thermoplastic elastomer molded product, which has been a problem in the past, but also to impart water / oil repellency and form a surface with a very low dynamic friction coefficient. Thus, the present invention has been completed.

That is, the present invention relates to a fluorinated alkyl group-containing (meth) acrylate monomer (A) represented by the following general formula and a straight-chain or branched alkyl having 10 to 30 carbon atoms. A copolymer (I) and a thermoplastic elastomer (II), characterized by containing a non-fluorine (meth) acrylate monomer (B) as a copolymer component as a copolymer component.
And a thermoplastic elastomer composition containing:

[0010]

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[However, Rf is a fluorinated alkyl group having 4 to 16 carbon atoms or 4 to 1 carbon atoms including ether oxygen.
6 is a fluorinated alkyl group, and X is a divalent linking group.

[0012]

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(R ′ is H or an alkyl group having 1 to 3 carbon atoms) or —CH ₂ —, — (CH ₂ ) ₂ ——CH ₂ C (O
H) CH ₂ - and and, R represents H, CH ₃ -, it is Cl, F, or CN. ] Is provided.

It is also preferable to use a thermoplastic elastomer composition in which the fluorinated alkyl group-containing (meth) acrylate monomer (A) unit accounts for 25 to 80% by weight of the copolymer (I). The polymer (I) is a thermoplastic elastomer composition having a number average molecular weight of 1,000 to 1,000,000 in terms of polystyrene by gel permeation chromatography. Preferably, the copolymer (I) is made of fluorine. Alkylated group-containing (meth) acrylate monomer (A) and an ester moiety substituent having 10 to 3 carbon atoms
A thermoplastic elastomer composition containing a binary copolymer with a non-fluorine (meth) acrylate (B) which is a linear or branched alkyl group of 0, preferably the copolymer (I) The thermoplastic elastomer composition is blended with 0.05 to 20 parts by weight based on 100 parts by weight of the thermoplastic elastomer (II).

In the present invention, (meth) acrylic
The term "acrylate" is a general term for an acrylate compound and a methacrylate compound.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As the thermoplastic elastomer of the present invention, known and commonly used ones can be used. Specifically, styrene-based,
Various elastomers such as olefin, polyester, polyurethane, polyamide, and PVC are exemplified.

More specifically, examples of the polyester elastomer include low molecular weight diols, dicarboxylic acids,
Aliphatic polyether and / or aliphatic polyester,
Alternatively, those obtained by reacting these ester-forming derivatives as essential components can be used.

The polyester elastomer generally comprises a hard segment and a soft segment in view of the molecular structure. The hard segment is a unit composed of a low molecular weight diol, a dicarboxylic acid and / or an alkyl ester thereof, and the soft segment is a unit composed of an aliphatic polyether and / or an aliphatic polyester and a dicarboxylic acid and / or an alkyl ester thereof. Consists of In the polyester elastomer used in the present invention, the ratio of the soft segment and the hard segment in the molecular structure is the former / the latter (weight ratio) = 1.
Those having a ratio of 0/90 to 0/100 are preferred.

Examples of the low molecular weight diol include alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, decamethylene glycol, and p-xylylene. Glycol and cyclohexanedimethanol.

Examples of the dicarboxylic acid and / or alkyl ester include terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, bis (p-carboxyphenyl) methane, and 4,4-sulfonyldibenzoic acid; Examples thereof include aliphatic dicarboxylic acids and dialkyl esters thereof. Examples of the aliphatic polyether and / or aliphatic polyester include, for example, poly (oxyalkylene) glycols such as poly (oxyethylene) glycol, poly (oxypropylene) glycol, and poly (oxytetramethylene) glycol; A) mixtures or copolymers of glycols, poly-ε caprolactone, polyesters obtained from aliphatic dicarboxylic acids having 2 to 12 carbon atoms and aliphatic glycols having 2 to 10 carbon atoms, for example, polyethylene adipate, polytetramethylene adipate, polyethylene seba Kate, polyneopentyl sebacate, polytetramethylene dodecane, polytetramethylene acetate, polyhexamethylene acetate, etc., and a combination of the above aliphatic polyester and aliphatic polyether Combined polyester polyether copolymer, and the like.

The polyurethane elastomer used in the present invention includes polyols having a molecular weight of 500 to 6,000, for example, bifunctional polyesters, polyethers, polycarbonates and block copolymers thereof, and organic diisocyanates having a molecular weight of 500 or less. For example, diphenylmethane diisocyanate (abbreviated as MDI), tolylene diisocyanate (TDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPD)
A polymer obtained by a polyaddition reaction of I) or the like with a chain extender, for example, with glycol, triol, diamine, hydrazine, water or the like can be used.

Further, the olefin elastomer used in the present invention includes a crystalline polypropylene resin and ethylene / α-olefin copolymer rubber or ethylene / α.
-Consists of olefin / non-conjugated diene copolymer rubber,
In the olefin-based elastomer, these components exist in a partially cross-linked state, and the weight ratio of the crystalline polypropylene resin to the olefin-based rubber (crystalline polypropylene resin / olefin-based rubber) is 70/30 to
It is in the range of 10/90. More specific examples of the olefin-based elastomer preferably used in the present invention include 60 to 10 parts by weight of a crystalline polypropylene resin and ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber as the olefin rubber. 4
0 to 90 parts by weight [the total amount of the crystalline polypropylene resin and the olefin-based rubber is 100 parts by weight], 5 to 40 parts by weight of a rubber other than the olefin-based rubber, and / or 5 to 100 parts by weight of a mineral oil-based softening agent And a thermoplastic elastomer in which an olefin-based rubber is partially crosslinked.

The olefin elastomer used in the present invention can be obtained by dynamically heat-treating a blend containing a crystalline polyolefin resin and an olefin rubber in the presence of an organic peroxide.

As the above-mentioned organic peroxide, specifically,
Dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert- Butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl Peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

The fluorine (meth) acrylate monomer (A) of the present invention is represented by the following general formula.

[0026]

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[However, Rf is a fluorinated alkyl group having 4 to 16 carbon atoms or 4 to 1 carbon atoms including ether oxygen.
6 is a fluorinated alkyl group, and X is a divalent linking group.

[0028]

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(R ′ is H or an alkyl group having 1 to 3 carbon atoms) or —CH ₂ —, — (CH ₂ ) ₂ ——CH ₂ C (O
H) CH ₂ - and and, R represents H, CH ₃ -, it is Cl, F, or CN. Specific examples of the fluorinated (meth) acrylate monomer (A) include the following compounds.

A-1 C ₈ F ₁₇ CH ₂ CH ₂ OCOCH = CH ₂ a-2 C ₈ F ₁₇ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ a-3 C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = _{CH 2 a-4 C 10 F} 21 CH 2 CH 2 OCO (CH 3) = CH 2 a-5 C 4 F 9 CH 2 CH 2 OCOCH = CH 2 a-6 C 14 F 29 CH 2 CH 2 OCOC (CH ₃ ) = CH ₂ a-7 CF ₃ CF ₂ CH ₂ CH ₂ OCOCH = CH ₂ a-8 CF ₃ CF ₂ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ a-9 C ₈ F ₁₇ SO ₂ N ( _{C 3 H 7) CH 2 CH} 2 OCOCH = CH 2 a-10 C 8 F 17 SO 2 NHCH 2 CH 2 OCOC (CH 3) = CH 2 a-11 C 8 F 17 SO 2 N (CH 3) CH 2 _{CH 2 OCOCH = CH 2 a-} 12 C 8 F 17 SO 2 N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2 a-13 C 7 F 15 SO 2 NHCH 2 CH 2 O _{OCH = CH 2 a-14 C} 12 F 25 SO 2 N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2 a-15 C 4 F 9 SO 2 NHCH 2 CH 2 OCOCH = CH 2 a-16 _{C 4 F 9 SO 2 NHCH 2} CH 2 OCOC (CH 3) = CH 2 a-17 C 8 F 17 CH 2 CH 2 OCOCF = CH 2 a-18 C 8 F 17 CH 2 CH 2 OCOCCl = CH 2 a- 19 C ₈ F ₁₇ CH ₂ CH ₂ OCOC (CN) = CH ₂ a-20 C ₆ F ₁₃ CH ₂ CH ₂ OCOCF = CH ₂ a-21 C ₆ F ₁₃ CH ₂ CH ₂ OCOCCl = CH ₂ a-22 C _{6 F 13 CH 2 CH 2 OCOC} (CN) = CH 2 a-23 C 8 F 17 CH 2 CH (OH) CH 2 OCOCH = CH 2 a-24 C 6 F 13 CH 2 CH (OH) CH 2 OCOCH = _{CH 2 a-25 C 8 F} 17 CH 2 CH (OH) CH 2 OCOC (CH 3) = CH 2 a-26 C 6 F 13 CH 2 CH (OH) CH ₂ OCOC (CH ₃ ) = CH ₂ a-27 CF ₃ (CF (CF ₃ ) O) ₄ CH ₂ CH ₂ OCOCH = CH ₂ Fluorine (meth) acrylates (A) have different Rf chain lengths. A mixture of two or more types of compounds may be used, or a mixture of two or more types of compounds having different structures at portions other than the Rf chain length may be used. Further, the Rf chain length is different,
Also, a mixture of two or more compounds having different structures other than the Rf chain length may be used. It should be noted that the present invention is not limited to the above specific examples.

In the present invention, the fluorinated alkyl group-containing (meth) acrylate monomer (A) in the copolymer (I)
Has a perfluoroalkyl group with a very high surface orientation and plays a leading role in the segregation of the surface of the copolymer, and is a monomer component essential for expressing the surface modification effect. If this is missing, the above performance will be poor.

From the viewpoint of modifying the surface of the thermoplastic resin molded product according to the present invention, the fluorine-containing (meth) acrylate (A) is one in which all of the hydrogen atoms of the fluorinated alkyl group are replaced by fluorine atoms. Is preferable, and the number of carbon atoms of the fluorinated alkyl group is preferably 6 or more, and more preferably 8 or more.

The non-fluorinated (meth) acrylate monomer (B) of the present invention has an ester substituent having 1 carbon atom.
If it is a thing of 0-30, there is no limitation at all,
For example, those already known in the art include decyl (meth) acrylate, isodecyl (meth) acrylate,
Lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, aliphatic ester (meth) acrylate such as behenyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, etc. having a bridge-like bond (meth)
Acrylates are mentioned. It is needless to say that the present invention is not limited by these specific examples.

In the present invention, a non-fluorine (meth) -based (meth) acrylic resin is used because it exhibits water and oil repellency, low friction, non-adhesion, antifouling, and improved hydrolysis resistance on the surface of the thermoplastic resin molded product. As the acrylate monomer (B), those having 15 to 25 carbon atoms in the ester substituent are preferable, and those having 18 carbon atoms are more preferable.
To 22 are particularly preferred.

Specific examples thereof include the following compounds. _{b-1 C 18 H 37 OCOCH} = CH 2 b-2 C 16 H 33 OCOCH = CH 2 b-3 C 16 H 33 OCOC (CH 3) = CH 2 b-4 C 20 H 41 OCOCH = CH 2 b- _{5 C 18 H 37 OCOC (CH} 3) = CH 2 b-6 C 15 H 31 OCOC (CH 3) = CH 2 b-7 C 19 H 39 OCOC (CH 3) = CH 2 b-8 C 22 H 45 OCOCH = CH ₂ b-9 C ₂₂ H ₄₅ OCOC (CH ₃ ) = CH ₂ Of course, the present invention is not limited by the above specific examples.

The copolymer (I) of the present invention comprises, as constituent monomers thereof, the (fluorinated) alkyl group-containing (meth) acrylate (A) and the non-fluorinated (meth) acrylate (B)
However, in order to achieve the object of the present invention, a copolymer of (A) and (B) is preferable.

The copolymer (I) according to the present invention has the above-mentioned fluorinated alkyl group as its constituent monomer for the purpose of adjusting the compatibility with the elastomer constituents and the performance as a surface modifier. In addition to the contained (meth) acrylate (A) and the non-fluorinated (meth) acrylate (B), the silicone-based monomer (C) and the known non-fluorinated (meth) acrylate (B) other than the (meth) acrylate (B) By copolymerizing the copolymerizable monomer (D), a multi-component copolymer can also be obtained.

The silicone-based monomer (C) is an α, β-unsaturated group, ie, a vinyl group, an acryloyl group, or the like at one or both ends of a polysiloxane chain via a divalent linking group.
Alternatively, it refers to a compound in which any one of methacryloyl groups is linked, and specific examples thereof include compounds represented by general formula (C-1)

[0039]

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[In the formula, R ₃ and R ₄ are an alkyl group having 1 to 20 carbon atoms or a phenyl group, which may be the same or different, or may be the same or different for each siloxy unit, and p is 3 X is an integer of from 0 to 520, q is 0 or 1, X ₂ is a divalent linking group, and —CH ₂ CH (OH) CH ₂ OCO—, — (CH ₂ )
_n1 NHCH ₂ CH (OH) CH ₂ OCO-,-(CH ₂ ) _n1 OCO-,-(CH ₂ ) _n1 -O- (CH
_{2) m1} OCO-, or _{-OCH 2 CH (OH) CH 2} OCO- [ where, n ₁ m ₁ is 2
6 to an integer. R ₁ is the same as described above, and Z ₁ is a methyl group, a phenyl group, or CH ₂ = C (R ₁ )-(X ₂ ) _q
-Yes. Or a compound represented by the general formula (C-
2)

[0041]

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[Wherein R ₅ , R ₅ ′, R ₅ ″, R ₆ ,
R ₆ ′, R ₆ ″, R ₇ , R ₇ ′, R ₇ ″ are an alkyl group or a phenyl group having 1 to 20 carbon atoms, which may be the same or different, and r, s, t are 0 or An integer of 1 to 200, which may be the same or different, and X ₂ , q,
R ₁ is as defined above. ] The compound represented by this is mentioned.

The following are examples of more specific silicone monomers.

[0044]

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[0045]

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[0046]

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[0047]

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Here, Me and Ph represent a methyl group and a phenyl group, respectively. As the ethylenically unsaturated group of the silicone-based monomer (C), any of a vinyl group, an acryloyl group, and a methacryloyl group is possible, but an acryloyl group or a methacryloyl group is excellent in terms of polymerization reactivity. Therefore, those containing these are particularly preferred. The silicone-based monomer (C) may be a mixture of two or more compounds having different structures.

Specific examples of known and commonly used copolymerizable monomers (D) other than the non-fluorinated (meth) acrylate monomers (B) include the following. That is, styrene, nuclear-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinyl fatty acid such as vinyl sulfonic acid and vinyl acetate, and α, β-ethylenically unsaturated carboxylic acid, ie, acrylic acid Mono- or divalent carboxylic acids such as methacrylic acid, maleic acid, fumaric acid, and itaconic acid;
-As a derivative of an ethylenically unsaturated carboxylic acid, a (meth) acrylate having an alkyl group having 1 to 10 carbon atoms, that is, methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl ester of (meth) acrylic acid, C1-C10 hydroxyalkyl esters of (meth) acrylic acid, such as 2-hydroxyethyl ester, hydroxypropyl ester, hydroxybutyl ester, etc., and (meth) acrylic acid C1-C10 aminoalkyl esters, namely dimethyl Aminoethyl ester,
Diethylaminoethyl ester, diethylaminopropyl ester, etc., and (meth) acrylic acid having 3 to 3 carbon atoms
18 ether oxygen-containing alkyl esters such as methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbyl ester, butylcarbyl ester, etc., and polyethylene glycol and polypropylene glycol having a polymerization degree of 1-100. Mono (meth) acrylates or di (meth) acrylates of polyalkylene glycols such as ethylene glycol, or polyethylene having a degree of polymerization of 1 to 100 and having a terminal capped by an alkyl group having 1 to 6 carbon atoms. Mono (meth) acrylic acid esters of polyalkylene glycols such as glycols and polypropylene glycols; and alkyl vinyl ethers having 1 to 18 alkyl carbon atoms, for example, methyl vinyl ether, propyl vinyl ether, dodecyl Vinyl ether such as (meth) glycidyl esters of acrylic acid, i.e. glycidyl methacrylate, glycidyl acrylate, addition Sartomer styrene macromonomer 4500, Shin-Nakamura Chemical Co. (Ltd.) N
Macromonomers such as K-ester M-230G,
-Methacryloxypropylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, etc. As monomers having a silane coupling group and a monomer having a polar group, particularly an anionic group or a hydroxyl group, in the molecule, acrylic acid, methacrylic acid,
(Meth) acryloyloxyethyl succinic acid, 2-acrylamido-2-methylpropanesulfonic acid, partially sulfonated styrene, mono (acryloyloxyethyl) acid phosphate, mono (methacryloxyethyl) acid phosphate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like.

It goes without saying that the present invention is not limited by the above specific examples. The fluorinated alkyl group-containing ethylenically unsaturated monomer (A) according to the present invention and a non-fluorinated (meth) acrylate monomer in which the ester substituent is a linear or branched alkyl group having 10 to 30 carbon atoms The method for producing the copolymer (I), which comprises the copolymer (B) as a copolymer component, is not particularly limited, and a known method can be used. That is, based on a polymerization mechanism such as a radical polymerization method, a cation polymerization method, or an anion polymerization method, a solution polymerization method, a bulk polymerization method, and a emulsion polymerization method can be used, but the radical polymerization method is particularly simple.
Industrially preferred. In this case, as the polymerization initiator, those known in the art can be used.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide and diacyl peroxide, azo compounds such as azobisisobutyronitrile and phenylazotriphenylmethane, and metal chelate compounds such as Mn (acac) 3. And the like. Lauryl mercaptan, if necessary, 2-
A chain transfer agent such as mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, and a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane are used in combination with the chain transfer agent. It is possible. The fluorine-based random or block copolymer according to the present invention can also be obtained by photopolymerization in the presence of a photosensitizer or a photoinitiator or polymerization using radiation or heat as an energy source.

The polymerization can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones, such as tetrahydrofuran, dioxane, dimethyl ether, methyl ethyl ether, etc., esters such as methyl acetate, ethyl acetate, butyl acetate, polar solvents such as dimethyl formamide, dimethyl sulfoxide, 1,1,1-trichloroethane , Chloroform, dichloroethane, perchlorethylene, chlorinated solvents such as carbon tetrachloride, hexane, heptane, octane Aliphatic hydrocarbons such as kerosene, aromatic hydrocarbons such as toluene, xylene, and benzene; mixed aromatic / aliphatic hydrocarbons such as terpenes and mineral spirits; and perfluorooctane and perfluorotri-n- Examples include fluorinated inert liquids such as butylamine, and fluorinated ethers such as C ₄ F ₉ OCH ₃ and C ₄ F ₉ OC ₂ H ₅ .

In the copolymer (I) according to the present invention, the copolymerization ratio between the fluorinated alkyl group-containing (meth) acrylate monomer (A) and the non-fluorine (meth) acrylate monomer (B) Is not particularly limited, but is preferably 25:75 to 90:10 by weight ratio, and the surface of the thermoplastic resin molded product according to the present invention has water and oil repellency, low friction, non-adhesion, and stain resistance. In order to effectively exhibit effects such as improvement in the properties and hydrolysis resistance, 40:60 to 80:20 is more preferable. The copolymerization ratio of the fluorinated alkyl group-containing (meth) acrylate monomer (A) in the copolymer (I) is 25.
If the amount is less than parts by weight, the copolymer (I) on the molded product surface
Surface segregation is not sufficient and the desired effect cannot be obtained,
On the other hand, if it is more than 90 parts by weight, the resin compatibility deteriorates and the appearance of the molded product is impaired, which is not preferable.

In the fluorine-based copolymer (I) according to the present invention, the copolymerizable monomer other than the silicone-based monomer (C) and the non-fluorinated (meth) acrylate monomer (B) are used. When the known and commonly used comonomer (D) is introduced, the weight ratio of (C) or (D) to (A) + (B) is 100: 0 to 30:70, and 100: 0.
~ 70: 30 is particularly preferred.

The molecular weight of the fluorine-based copolymer (I) according to the present invention is such that the number average molecular weight in terms of polystyrene is 1,1.
000 to 1,000,000, and the surface of the thermoplastic resin molded product according to the present invention has water / oil repellency, low friction, non-adhesiveness,
It is more preferably from 1,000 to 200,000, particularly preferably from 1,000 to 100,000, from the viewpoint of effectively exhibiting effects such as improvement of antifouling property and hydrolysis resistance.

The amount of the copolymer (I) according to the present invention when internally added to the thermoplastic elastomer composition is not particularly limited.
The amount is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 5 parts by weight with respect to 0 parts by weight.

If the amount is less than 0.05 part by weight, the effect of modifying the surface is not sufficient, and if it is more than 20 parts by weight, the strength and moldability of the thermoplastic elastomer composition of the present invention are undesirably reduced.

In the present invention, a known inorganic filler can be added to the thermoplastic elastomer composition, if necessary, as long as the object of the present invention is not impaired. Specific examples of the inorganic filler include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, molybdenum disulfide, and glass. Fibers, glass spheres, shirasu balloons, graphite, alumina and the like can be mentioned. The amount of the inorganic filler to be added is preferably 0.1 to 80% by weight in the composition of the present invention.

Further, other resins can be added as long as the object of the present invention is not impaired. Examples of the resin include modified polyphenylene ethers such as polyphenylene ether and styrene graft, polyarylate, polyamide, polybutylene terephthalate, polyethylene terephthalate, poly 1.4-cyclohexane dimethylene terephthalate, polycarbonate, various liquid crystal polymers, polysulfone, Polyether sulfone,
Polyallyl sulfone, polyether ketone, polyether ether ketone, polyethylene, polypropylene, polymethylpentene, polystyrene, hydrogenated styrene butadiene rubber, ethylene propylene rubber, polyisoprene,
Thermoplastic or thermosetting resins such as polyisobutylene, polybutene, phenoxy resin, epoxy resin, polyimide, polyamide imide, urea resin, phenol resin, DAP resin, fluorinated olefin resin, and silicone resin. Known heat stabilizers, anti-aging agents, and weather stabilizers include phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, and benzotriazole-based stabilizers. Knox 1010 [manufactured by Ciba Geigy Corporation],
Sanol LS-765 (manufactured by Sankyo), Chemisorb 74 (Chempro Chemical) and the like.

In the present invention, known additives can be added to the thermoplastic elastomer composition, if necessary, as long as the object of the present invention is not impaired. For example, phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based heat stabilizers, anti-aging agents, weather resistance stabilizers, and antistatic agents,
Lubricants such as metal soaps and waxes, silanes, titanates, zirconates, zircoaluminates, surface treatment agents such as aluminum chelate compound-based coupling agents, and oxides, hydroxides or carbonates of alkali metals or alkaline earth metals Corrosion inhibitors, coloring agents, nucleating agents and the like can be added in an amount of 0.01 to 10% by weight based on the composition of the present invention.

The thermoplastic elastomer composition of the present invention can be produced by kneading and mixing by known methods such as an extruder, an injection molding machine and various mixers.
A method in which the copolymer (I) according to the present invention is kneaded with an extruder to produce high-concentration pellets, and then mixed with pellets containing no copolymer (I) for injection molding, or immediately before injection molding. Method of directly mixing and molding into pellets,
That is, in any of the dry blending methods, the copolymer (I) according to the present invention is uniformly dispersed in the thermoplastic elastomer,
The above-described performance can be exhibited.

The thermoplastic elastomer composition of the present invention comprises:
It can be applied without problems in the fields conventionally used. For example, automotive applications such as bumpers, interior materials, gaskets, hoses, various protectors, syringe gaskets,
Medical and food related parts such as health appliances, belts, civil engineering and construction materials, video, audio parts, hoses, packings,
General and industrial parts such as watch bands and scuba diving equipment.

Among them, it is particularly suitable for parts requiring water- and oil-repellency, low friction, non-adhesion, and hydrolysis resistance. For example, a stabilizer which is one of automobile parts for preventing squeals between parts is required. Can be used for bushes.

[0064]

EXAMPLES The present invention will be described in more detail with reference to specific synthesis examples and examples according to the present invention, but it is needless to say that the present invention is not limited by these specific examples and the like.

Synthesis Example 1 A fluorine-containing (meth) acrylate monomer (a-1) 7 was placed in a glass flask equipped with a stirrer, a condenser, and a thermometer.
0 parts by weight and a non-fluorinated (meth) acrylate monomer (b
-1) 30 parts by weight and 233 parts by weight of a terpene are charged, and 1 part by weight of azobisisobutyronitrile (hereinafter, abbreviated as AIBN) as a polymerization initiator and 1 part by weight of a serial transfer agent in a nitrogen gas stream under reflux. After adding 2 parts by weight of lauryl mercaptan, the temperature was raised to 85 ° C. for 30 minutes, and a copolymerization reaction was performed at the same temperature for 7 hours. The obtained copolymer had a solid content of 30.2% by weight. The solvent of this solution was removed with a rotary evaporator, and the obtained solid was pulverized to obtain a fine powder.

The molecular weight of this polymer in terms of polystyrene by a gel permeation graph (hereinafter abbreviated as GPC) was Mn = 5,000. This copolymer is referred to as a fluoropolymer 1.

Synthesis Examples 2 to 10 Various fluorinated alkyl group-containing (meth) acrylate monomers (A), non-fluorinated (meth) acrylate monomers (B), silicone monomers (C) And other known and commonly used copolymerized monomers (D) and chain transfer agents are shown in Tables 1 and 2
A fluorine compound was obtained in the same manner as in Synthesis Example 1 except that the fluorine compound was used in the proportions shown in Table 1. The results of the molecular weight measurement of these polymers are shown in Tables 1 and 2. In Tables 1 and 2, the charging ratios of the raw materials are parts by weight, and the symbols of the raw materials indicate the compounds described in the text.

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[Table 1]

[0069]

[Table 2]

Examples 1 to 18 Mirastomer 5030N (manufactured by Mitsui Petrochemical Industries, Ltd.) was used as the olefin-based thermoplastic elastomer, and the fluorine-based copolymer of Synthesis Examples 1 to 17 was added to the olefin-based thermoplastic elastomer at a predetermined concentration. Compounded and fed to an extruder and pelletized at 210 ° C. The pellets were subjected to measurement of characteristic values using test pieces obtained by injection molding under the following conditions. Table 3 shows the addition amount of the fluorine-based copolymer and the measurement results of the characteristic values.

Injection molding machine: Niigata Iron Works NN50HS3000 Injection molding condition: Cylinder temperature 200 to 220 ° C., mold temperature 40 ° C. Comparative Example 1 In general, heat was used instead of the fluorine-based copolymer used in Example 1. Except that the metal soap used for the purpose of detackifying the surface of the plastic elastomer was added, the same operation as in Example 1 was performed, and the characteristic values of the obtained test pieces were measured.

Comparative Example 2 The same operation as in Example 1 was carried out except that no fluorine-based copolymer was used, and the characteristic values of the obtained test pieces were measured. Table 3 shows the measurement results of the characteristic values.

<Test Method and Evaluation Criteria> (1) Mechanical Properties Tensile strength at break, elongation at break, hardness
The measurement was performed based on 01. (2) Water and oil repellency The contact angle when water and n-dodecane droplets were dropped on the surface of the test piece obtained as described above was measured using an automatic contact angle meter CA.
It measured using the -Z type (made by Kyowa Interface Science Co., Ltd.), and evaluated it numerically. (3) Low friction property The surface of the test piece obtained as described above was 30 × 30 mm
Was made to contact with each other and a dynamic friction coefficient when a load of 200 g was applied was measured with a HEIDON-14 type surface property measuring instrument. (4) Non-adhesiveness The test pieces obtained as described above were superimposed on each other, and 100 kg was applied with a hot-air dryer while applying a load of 1 kg from above.
The strength at the time of peeling after promoting adhesion under the condition of ° C. × 24 hours was confirmed.

：: Adhesive strength is weak. Δ: The adhesive strength is slightly strong. ×: Strong adhesion.

[0075]

[Table 3]

Examples 19 to 36 Pandex T as a urethane-based thermoplastic elastomer
-8190 (manufactured by Dainippon Ink and Chemicals, Inc.), and the fluorine-based copolymers of Synthesis Examples 1 to 17 were blended so as to have a predetermined concentration, supplied to an extruder, and heated to 200 ° C.
And pelletized. The pellets were subjected to measurement of characteristic values using test pieces obtained by injection molding under the following conditions. Table 4 shows the amount of the fluorocopolymer added and the measurement results of the characteristic values.

Injection molding machine: Model NN50HS3000 manufactured by Niigata Iron Works Injection molding conditions: Cylinder temperature 190-210 ° C., mold temperature 40 ° C. Comparative Example 3 In place of the fluorine-based copolymer used in Example 12, heat was generally used. Except that ethylene bisamide (KAO EBF) used for the purpose of detackification of the surface of the plastic elastomer was added, the same operation as in Example 12 was performed, and the characteristic values of the obtained test pieces were measured.

Comparative Example 4 The same operation as in Example 12 was carried out except that the fluorine-based copolymer was not used, and the characteristic values of the obtained test pieces were measured. Table 4 shows the amount of the fluorocopolymer added and the measurement results of the characteristic values.

<Test Method and Evaluation Criteria> (1) Mechanical Properties Based on JIS K7311, 100% and 300% modulus, tensile strength,
The elongation, tear strength and hardness (Shore A) were measured. (2) Flow characteristics Using a Koka type flow tester, the temperature rise rate from 150 ° C to 3
Flow start temperature under conditions of ° C / min, load of 30 kg, and 1
The resin viscosity at 80 ° C. was compared. (3) Surface Properties The water- and oil-repellency, low friction, and non-adhesion were evaluated in the same manner as described above.

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[Table 4]

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According to the present invention, the present invention provides a method for molding a thermoplastic elastomer obtained from a thermoplastic elastomer while maintaining the moldability of the thermoplastic elastomer, particularly the melt fluidity, when the thermoplastic elastomer is subjected to thermoforming such as extrusion molding and injection molding. Adhesion, which is a drawback, can be significantly improved, and high functions such as low friction of the surface and water / oil repellency can be imparted.

Claims (5)

[Claims] (1) A fluorinated alkyl group-containing (meth) acrylate monomer (A) represented by the following general formula and the ester substituent is a linear or branched alkyl group having 10 to 30 carbon atoms. Non-fluorine (meth) acrylate monomer (B)
A thermoplastic elastomer composition comprising a copolymer (I) and a thermoplastic elastomer (II), characterized by containing as a copolymer component. Embedded image [However, Rf is a fluorinated alkyl group having 4 to 16 carbon atoms,
Or a fluorinated alkyl group having 4 to 16 carbon atoms containing ether oxygen, and X is a divalent linking group. (R 'is H or an alkyl group having 1 to 3 carbon atoms) or-
CH ₂ —, — (CH ₂ ) ₂ ——CH ₂ C (OH) CH ₂ —, and R is H, CH ₃ —, Cl, F, or CN. ] 2. The copolymer (I) contains 25 to 8 units of the fluorinated alkyl group-containing (meth) acrylate monomer (A).
The thermoplastic elastomer composition according to claim 1, wherein the amount is 0% by weight. 3. The thermoplastic elastomer composition according to claim 1, wherein the number average molecular weight of the copolymer (I) is 1,000 to 1,000,000 in terms of polystyrene by gel permeation chromatography. 4. The copolymer (I) is a (meth) acrylate monomer (A) containing a fluorinated alkyl group and a straight-chain or branched alkyl group having 10 to 30 carbon atoms in the ester substituent. The thermoplastic elastomer composition according to any one of claims 1 to 3, comprising a binary copolymer with a non-fluorine (meth) acrylate (B). 5. The method according to claim 1, wherein the copolymer (I) is blended in an amount of 0.05 to 20 parts by weight based on 100 parts by weight of the thermoplastic elastomer (II).
Item 10. The thermoplastic elastomer composition according to Item 8.