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WO2007148636A1 - Composition élastomère thermoplastique - Google Patents

Composition élastomère thermoplastique Download PDF

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Publication number
WO2007148636A1
WO2007148636A1 PCT/JP2007/062181 JP2007062181W WO2007148636A1 WO 2007148636 A1 WO2007148636 A1 WO 2007148636A1 JP 2007062181 W JP2007062181 W JP 2007062181W WO 2007148636 A1 WO2007148636 A1 WO 2007148636A1
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Prior art keywords
thermoplastic elastomer
group
elastomer composition
acrylic
weight
Prior art date
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PCT/JP2007/062181
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English (en)
Japanese (ja)
Inventor
Akio Taniguchi
Takeshi Chiba
Yutaka Kaneda
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Kaneka Corp
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Kaneka Corp
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Priority to JP2008522439A priority Critical patent/JPWO2007148636A1/ja
Publication of WO2007148636A1 publication Critical patent/WO2007148636A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a thermoplastic elastomer composition, a powder slush molding material using the composition, and an automobile interior skin obtained by powder slush molding.
  • an acrylic block copolymer having methyl methacrylate as a hard segment and butyl acrylate as a soft segment has characteristics as a thermoplastic elastomer.
  • thermoplastic elastomer By appropriately selecting the components constituting the block body, it is possible to give an extremely flexible elastomer compared to other thermoplastic elastomers such as styrene block bodies.
  • the acrylic block copolymer has excellent characteristics such as weather resistance, heat resistance, and oil resistance. Furthermore, as described in Patent Document 1, the i-ferter method is used. The mechanical properties (tensile strength, elongation, etc.) manufactured in
  • a powder slash molding method which is a powder molding method using a soft powder material.
  • This method is widely used for molding automotive interior skin materials such as instrument panels, console boxes and door trims. This is because, according to the powder one slash molding method, a product with a soft feel is obtained, and the skin texture is stitched. Can be provided in the product, the degree of freedom of design is large, and the design is good. Unlike other molding methods such as injection molding and compression molding, this molding method does not apply shaping pressure during molding. For this reason, it is necessary to uniformly adhere the powder material to a mold having a complicated shape during molding, and the powder is required to have excellent fluidity.
  • Patent Documents 2 and 3 introduce a carboxyl group or an acid anhydride group into an acrylic block copolymer to increase the molecular weight or a crosslinking reaction during molding, thereby achieving both melt fluidity and heat resistance.
  • the material which aimed at is proposed! RU
  • Patent Document 1 JP-A-1-26619
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2006-104410
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2006-104419
  • the present invention is a thermoplastic elastomer excellent in storage stability and melt fluidity at the time of molding, and further in heat resistance, oil resistance, chemical resistance, adhesiveness and flexibility of the obtained molded product.
  • the purpose is to obtain a composition.
  • any acrylic block containing a hydroxyl group, an acid anhydride group, or a carboxyl group and having a predetermined structure As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that any acrylic block containing a hydroxyl group, an acid anhydride group, or a carboxyl group and having a predetermined structure. In order to solve the present invention, the inventors have found that the above-mentioned problems can be effectively solved by using a composition containing a polymer and a compound having an epoxy group and capable of being increased in molecular weight or crosslinked during molding. It came.
  • the present invention provides: (I) A methacrylic polymer block (a) having a methacrylic monomer as a main component and a glass transition temperature of 25 to 130 ° C. (a) 10 to 60% by weight, an acrylic polymer block (b) 90 to 40% by weight, and at least one polymer block selected from the group consisting of a hydroxyl group, an acid anhydride group, and a carboxyl group is included in at least one of the blocks (a) and (b).
  • a thermoplastic elastomer composition comprising a compound (B) having a reactive functional group (d) and a thermal latent catalyst (C),
  • R 1 represents hydrogen or a methyl group
  • p and m each represent an integer of 1 or more.
  • thermoplastic elastomer composition according to (II) or (III), wherein R 1 and R 2 are both hydrogen,
  • thermoplastic elastomer composition force The thermoplastic elastomer composition according to any one of (II) to (IV), which is present in the acrylic polymer block (b) ,
  • thermoplastic elastomer composition according to (I), characterized in that:
  • thermoplastic elastomer composition according to any one of (I) to (VII),
  • thermoplastic elastomer composition according to any one of ( ⁇ ) to (IX), wherein the compound ( ⁇ ) has an acrylic polymer strength
  • thermoplastic elastomer according to any one of ⁇ ) to ( ⁇ ), which is a group force consisting of an epoxy group, a carboxyl group, a hydroxyl group and an amino group, selected from ⁇ ) to ( ⁇ )
  • ⁇ a group force consisting of an epoxy group, a carboxyl group, a hydroxyl group and an amino group, selected from ⁇ ) to ( ⁇ )
  • thermoplastic elastomer according to any one of (I) to (XIV), wherein the thermal latent catalyst (C) exhibits activity when heated at 60 ° C or higher.
  • thermoplastic elastomer composition according to any one of (I) to (XV), wherein the heat latent catalyst (C) is a metal salt compound,
  • the heat latent catalyst (C) is characterized in that it is a compound comprising a fatty acid having 4 to 16 carbon atoms or a diketone compound having 2 to 16 carbon atoms and zinc ( Any force of I) to (XVI)
  • the thermoplastic elastomer composition according to paragraph 1 is characterized in that it is a compound comprising a fatty acid having 4 to 16 carbon atoms or a diketone compound having 2 to 16 carbon atoms and zinc ( Any force of I) to (XVI)
  • the thermoplastic elastomer composition according to paragraph 1
  • thermoplastic elastomer according to any one of ⁇ ) to ( ⁇ ), wherein the thermal latent catalyst (C) is zinc laurate or bis (acetylacetonato) zinc.
  • thermal latent catalyst (C) is zinc laurate or bis (acetylacetonato) zinc.
  • thermoplastic elastomer composition according to any one of (i) to (XVIII), wherein the heat latent catalyst (C) is zinc laurate,
  • thermoplastic elastomer composition according to any one of (1) to (XVI), wherein the heat latent catalyst (C) is zinc tert-butylbenzoate,
  • thermoplastic elastomer composition Any one of (I) to (XX), characterized in that it contains 0.01 to 5 parts by weight of the thermal latent catalyst (C) with respect to 100 parts by weight.
  • thermoplastic elastomer composition according to claim 1,
  • thermoplastic elastomer composition for powder slush molding comprising the composition according to any one of ( ⁇ ) to ( ⁇ ),
  • thermoplastic slush molding of the thermoplastic elastomer composition according to any one of (i) to (ii),
  • thermoplastic elastomer composition A skin for automobile interior characterized by being formed by powder slush molding of the thermoplastic elastomer composition according to any one of (i) to (ii). In between.
  • thermoplastic elastomer composition according to the present invention is excellent in moldability, heat resistance and storage stability. For this reason, the composition of the present invention can be suitably used for powder slush molding, and a molded article having stable quality can be obtained.
  • the structure of the functional group (c) in the acrylic block copolymer (A) excellent storage stability with almost no restrictions on storage of the thermoplastic elastomer can be achieved.
  • weather resistance, oil resistance, and chemical resistance can be selected by appropriately selecting the molecular weight of the acrylic block copolymer (A), the monomer component, the compound (B), the type of the thermal latent catalyst (C), etc. It is possible to obtain a composition having excellent properties, adhesiveness, flexibility and abrasion resistance.
  • FIG. 1 is a schematic diagram of a scratch resistance evaluation test.
  • thermoplastic elastomer composition of the present invention comprises an acryl-based block copolymer (A) having a predetermined structure described below, and one or more reactive functional groups in one molecule. It comprises a compound (B) having (d) and a thermal latent catalyst (C).
  • the reactive functional group (d) in the compound (B) is a hydroxyl group, an acid anhydride group, which is the functional group (c) in the acrylic block copolymer (A).
  • the thermal latent catalyst (C) effectively promotes the reaction as a reaction accelerator.
  • the type of the heat latent catalyst (C) it is possible to ensure secondary workability such as adhesion.
  • the thermal latent catalyst (C) used in the present invention is a catalyst that exhibits higher activity when heated at a predetermined temperature (preferably 60 ° C. or higher).
  • the reason for using the thermal latent catalyst (C) is that if a normal catalyst such as an amine compound is used, the functional group (d) in the compound (B) and the functional group in the copolymer (A) described above are used.
  • the purpose is to prevent the cross-linking reaction by the group (c) from proceeding except at the time of thermoforming, that is, storage before molding. If the cross-linking reaction proceeds during storage before forming, the melt flowability of the thermoplastic elastomer is lowered, which causes deterioration of moldability.
  • the thermal latent catalyst (C) As the functional group (c) in the copolymer (A), a hydroxyl group that is less active than the carboxyl group is selected, and further, a hydroxyl group that is sterically protected by a nearby structure described later is selected. Is preferred.
  • (A) is a general formula (1) containing 1.0 or more hydroxyl groups per molecule on average
  • R 1 represents hydrogen or a methyl group
  • p and m each represent an integer of 1 or more
  • a monomer unit (X) a unit (X) and a unit ( At least one on each side of (X), close to unit (X)
  • R 2 represents hydrogen or a methyl group.
  • Q and n are each an integer of 1 or more, and n> m + 1, q> p.) ).
  • the side chain of the monomer unit (y) (ester chain (one COO (CH) — H)) is the monomer unit. Since the side chain of (x) (ester chain (one COO (CH) —OH)) is longer, the hydroxyl group of unit (X)
  • the structure of the acrylic block copolymer (A) of the present invention is not particularly limited, and may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof.
  • the structure of such a block copolymer may be appropriately selected according to the required physical properties of the acrylic block copolymer (A).
  • the linear block copolymer is selected. Polymer is preferred.
  • the linear block copolymer may have a structure (arrangement) that is out of alignment! /, but from the viewpoint of the physical properties of the linear block copolymer or the composition,
  • the methacrylic polymer block (a) is expressed as a and the acrylic polymer block (b) is expressed as b, (a -b) type, b— (a— b) type and (a— b) —
  • an a-b type diblock copolymer, an ab-a type triblock copolymer, or a mixture thereof is preferable in terms of easy handling during processing and the point of physical properties of the composition.
  • the functional group (c) selected from a hydroxyl group, an acid anhydride group and a carboxyl group contained in the acrylic block copolymer (A) is a methacrylic polymer block (a), an acrylic heavy polymer. One or more per molecule is introduced into one or both polymer blocks (b). When the number is two or more, the mode in which the monomer (e) having the functional group (c) is superposed can be random copolymerization or block copolymerization.
  • (aZz) — b—a type, (a / z) -b-(a / z) type, z— a— b— a type, z — A— b— a— z type, a— (bZ z) a type, a— b— z— a type, a — z— b— z— a type, (a / z)-(b / z) -(aZz) type, z-a-z-b-z-a-z type, etc. may be used.
  • z represents a polymer block obtained by polymerizing a monomer unit (e) having a functional group (c) or a monomer unit (f) having a hydroxyl group
  • (a / z) Means that the monomer unit (f) is copolymerized with the methacrylic polymer block ( a )
  • (bZz ) Means that the monomer unit (f) having a hydroxyl group is copolymerized with the acrylic polymer block (b).
  • the methacrylic polymer block (a) is! /
  • the site where z is contained and the manner in which it is contained should be appropriately set according to the purpose. Can do.
  • the molecular weight of the acrylic block copolymer (A) is not particularly limited, and may be determined from the molecular weights required for the methacrylic polymer block ( a ) and the acrylic polymer block (b), respectively. . However, if the molecular weight is small, sufficient mechanical properties as an elastomer may not be exhibited. Conversely, if the molecular weight is larger than necessary, the processing characteristics may deteriorate. In the case of the noder slash molding, since it is necessary to flow even under no pressure, if the molecular weight is large, the melt viscosity becomes high and the moldability may be deteriorated.
  • the molecular weight of the acrylic block copolymer (A) is 30,000 to 200,000 force S in terms of number average molecular weight S preferred ⁇ , more preferred ⁇ 35,000 to 150,000 More preferred, ⁇ or 40,000 to 100,000.
  • the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (MwZMn) of the acrylic block copolymer ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ) measured by gel permeation chromatography is not particularly limited. 1. Preferably it is 8 or less 1. More preferably, it is 5 or less. If Mw / Mn exceeds 1.8, the homogeneity of the acrylic block copolymer may deteriorate and the mechanical strength may decrease.
  • the composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is 5 for the methacrylic polymer block (a). It is preferable that the amount of the acrylic polymer block (b) is 95 to 10% by weight. From the viewpoint of maintaining the shape during molding and elasticity as an elastomer, the methacrylic polymer block (a) is 10 to 60% by weight, and the acrylic polymer block (b) is 90 to 40% by weight. More preferably, the methacrylic polymer block (a) is more preferably 15 to 50% by weight and the acrylic polymer block (b) is 3 ⁇ 4 to 50% by weight.
  • the proportion of the methacrylic polymer block (a) is less than 5% by weight, the shape tends to be difficult to retain during molding. If the proportion of the acrylic polymer block (b) is less than 10% by weight, the elastomer As an elastic material, there is a tendency for the flexibility and the meltability during molding to decrease. [0035] From the viewpoint of the hardness of the elastomer composition, when the proportion of the methacrylic polymer block (a) is small, the hardness is low, and when the proportion of the acrylic polymer block (b) is small, the hardness is low. The composition is appropriately set according to the required hardness of the elastomer composition. In terms of processing viewpoint, the viscosity is low when the proportion of (a) is small, and the viscosity tends to be high when the proportion of (b) is small. The composition is appropriately set according to the required processing characteristics. .
  • the relationship between the glass transition temperature of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) depends on the elastomer characteristics and rubber properties.
  • the glass transition temperature of one of the polymer blocks is preferably higher than the glass transition temperature of the other polymer block in terms of imparting, and the glass transition temperature of each block ( More preferably, the glass transition temperature of the methacrylic polymer block (a) is Tga, and the glass transition temperature of the acrylic polymer block (b) is Tgb).
  • the glass transition temperature (Tg) of the polymer (methacrylic polymer block (a) and acrylic polymer block (b)) is set according to the following Fox formula. This can be done by setting the ratio.
  • Tg represents the glass transition temperature of the polymer portion
  • Tgl, Tg2,..., Tgm represent the glass transition temperature of each polymerization monomer
  • Wl, W2,..., Wm represent the weight ratio of each polymerization monomer.
  • glass transition temperature of each polymerization monomer in the Fox formula for example, a value described in Polymer Handbook Third Edition (Wiley-Interscience 1989) may be used.
  • the glass transition temperature can be measured by DSC (differential scanning calorimetry) or tan ⁇ peak of dynamic viscoelasticity.
  • Methacrylic polymer block (a) and acrylic polymer block If the polarity of (b) is too close or the block monomer chain number is too small, The measured value may be different from the calculation formula by the Fox formula.
  • the acrylic block copolymer (A) having a hydroxyl group sterically protected by a neighboring structure as the functional group (c) has an average of 1.0 or more hydroxyl groups per molecule. It has a monomer unit (X) and at least two monomer units (y). At least one monomer unit ( y ) is present on both sides of the unit (X) in the vicinity of the unit (X), and sterically protects the hydroxyl group of the unit (X). For this purpose, the monomer unit (y) may or may not be present adjacent to the monomer unit (X).
  • r is a monomer other than units (X) and (y), for example, y—X—y, y—x—r—y, y—r—x—r—y They may be arranged as follows. Further, the plurality of monomer units (y) present in the acrylic block copolymer (A) do not necessarily have the same structure (the same value of n). Furthermore, as long as the above object can be achieved, the monomer unit (y) may exist at both ends of a continuous or non-continuous monomer unit (for example, y—X—X—y, y—X—r—X—y (r represents a monomer other than the units (X) and (y))).
  • n 4 is preferable in the general formula (2) from the viewpoint that flexibility can be imparted to the thermoplastic elastomer to be obtained and flexibility is available.
  • p> 2p from the viewpoint of storage stability.
  • a methacrylic polymer block (a) in which the relationship between p and q and m and n is combined with the entire acrylic block copolymer (A) is: Is preferably within the acrylic polymer block (b).
  • R 1 and R 2 in the general formula (1) and the general formula (2) are methyl groups.
  • R 1 and R 2 in general formula (1) and general formula (2) are preferably hydrogen! /.
  • R 1 is hydrogen, or units (X) and (y) are included in acrylic polymer block (b)
  • R 1 is a methyl group
  • the polymerization operation of the acrylic block copolymer (A) becomes complicated, or the methacrylic polymer block (a) and the acrylic polymer block (b)
  • the difference in glass transition temperature of the acrylic block copolymer (A) is reduced, and the rubber elasticity of the acrylic block copolymer (A) decreases. Tend to.
  • the monomer unit (X) having a hydroxyl group is an acrylic polymer block in that the rubber elasticity of the obtained molded article can be improved and the hysteresis loss can be reduced. (b) preferred to be present.
  • the methacrylic polymer block (a) is a block obtained by polymerizing a monomer having a methacrylic acid ester as a main component.
  • the methacrylic acid ester 50 100% by weight and a bule-based single copolymer copolymerizable therewith. It is preferable that the weight is 0-50% by weight.
  • the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, which is a characteristic of the methacrylic acid ester, may be impaired.
  • the methacrylic acid ester constituting the methacrylic polymer block (a) includes, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, Isobutyl acrylate, n-pentyl methacrylate, n-xyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, noel methacrylate, decyl methacrylate, meta Methacrylic acid aliphatic hydrocarbons such as dodecyl acrylate and stearyl methacrylate (e.g., alkyl having 1 to 18 carbon atoms); methacrylic acid alicyclic hydrocarbons such as cyclohexyl methacrylate and isobornyl methacrylate Esters; aralkyl methacrylates such
  • Trifluoromethyl methacrylate trifluoromethyl methyl methacrylate, 2-trifluoromethylethyl methacrylate, 2-trifluoroethyl methacrylate, 2-perfluoroethyl methacrylate Chill, 2-perfluoroethyl methacrylate, 2-perfluorobutylethyl methacrylate, 2-perfluoromethacrylate, perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, meta Acrylic acid 2-perfluoromethyl-2-perfluoroethylmethyl, methacrylic acid 2-perfluoro Examples thereof include fluorinated alkyl esters of methacrylic acid such as silethyl, 2-perfluorodecylethyl methacrylate, and 2-perfluorohexadecylethyl methacrylate. These can be used alone or in combination of two or more. Among these, methyl methacrylate is preferred in terms of processability,
  • Examples of bulle monomers that can be copolymerized with the methacrylic acid ester constituting the methacrylic polymer block (a) include acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated genes. Compounds, halogen-containing unsaturated compounds, vinyl ester compounds, maleimide compounds, and the like.
  • acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, and acrylic.
  • Acrylic aliphatic hydrocarbons such as n-heptyl acid, n-octyl acrylate, 2-ethylhexyl acrylate, noel acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, etc.
  • Examples of the aromatic alkenyl compound include styrene, ⁇ -methylstyrene, ⁇ -methylolstyrene, ⁇ -methoxystyrene, and the like.
  • Examples of the cyanide bur compound include acrylonitrile and meta-tallow-tolyl.
  • conjugation compound examples include butadiene and isoprene.
  • halogen-containing unsaturated compound examples include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
  • burester compound examples include butyl acetate, butyl propionate, butyl pivalate, benzoate, and vinyl cinnamate.
  • maleimide compounds include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenolmaleimide, and cyclohexylmaleimide. I can give you.
  • These compounds may be used alone or in combination of two or more.
  • These vinyl monomers are preferably selected from the viewpoints of adjusting the glass transition temperature required for the methacrylic polymer block (a) and compatibility with the acrylic block (b). .
  • the glass transition temperature of the methacrylic polymer block ( a ) is preferably from 25 to 130 ° C, more preferably from 50 to 130, from the viewpoint of thermal deformation and moldability of the elastomer composition. ° C, more preferably 70-100 ° C.
  • the methacrylic polymer block (a) is used for the purpose of adjusting the glass transition temperature of the methacrylic polymer block (a), which is desirably composed mainly of methyl methacrylate. It is preferable to polymerize at least one monomer selected from the group power of ethyl, n-butyl acrylate and 2-methoxyethyl acrylate. Of these, ethyl acrylate is particularly preferred from the viewpoint of compatibility with methyl methacrylate.
  • the Tga of the methacrylic polymer block (a) can be set by setting the weight ratio of the monomers in each polymer portion according to the Fox formula.
  • the unit polymer unit (X) having a hydroxyl group is contained in the methacrylic polymer block (a), from the viewpoint of storage stability and availability, n-butyl methacrylate, acrylic It is preferable that at least one monomer selected from the group power of acid n-ptylca is overlapped as a monomer unit (y). In the present application, even if all the monomers other than the monomer unit (X) in the methacrylic polymer block (a) are monomer units (y), some of the monomers are monomer units. Unit (y) may be used.
  • the acrylic polymer block (b) is a block obtained by polymerizing a monomer having an acrylic ester as a main component.
  • the acrylic ester block 50- L00% by weight and a bulle type copolymer copolymerizable therewith. It is preferable to consist of 0-50% by weight of the mass! /. If the proportion of acrylic acid ester is less than 50% by weight, the physical properties of the composition, particularly flexibility and oil resistance, which are characteristic when acrylic acid ester is used, may be impaired.
  • acrylic ester constituting the acrylic polymer block (b) for example, the same monomer as the acrylic ester exemplified as the monomer constituting the methacrylic polymer block ( a ) is used. I can give you. These can be used alone or in combination of two or more thereof. Among these, n-butyl acrylate is preferable from the viewpoint of rubber elasticity, low temperature characteristics and cost balance. Ethyl acrylate is preferred when oil resistance and mechanical properties are required. In addition, when it is necessary to impart low temperature characteristics and oil resistance and to improve the surface tackiness of the resin, acrylic acid-2-methoxyethyl is preferred. In addition, when a balance between oil resistance and low temperature characteristics is required, it is preferable to use a combination of ethyl acrylate, n-butyl acrylate and 2-methoxyethyl acrylate.
  • the acrylic polymer block (b) is at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate in terms of cost and physical property balance. body 50 to: L00 and weight%, and more preferably made of these with other copolymerizable acrylic acid ester and Z, or other Bulle monomer 50 to 0 weight 0/0 [0061]
  • Examples of the butyl monomer copolymerizable with the acrylate ester constituting the acrylic polymer block (b) include methacrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, and conjugate conjugates.
  • These bull monomers can be used alone or in combination of two or more. These bull monomers take into account the balance of the glass transition temperature and oil resistance required for the acrylic polymer block (b) and compatibility with the methacrylic polymer block (a). A preferable one is appropriately selected. For example, acrylonitrile may be copolymerized for the purpose of improving the oil resistance of the composition.
  • the glass transition temperature of the acrylic polymer block (b) is preferably 25 ° C or less, more preferably 0 ° C or less, from the viewpoint of flexibility of the elastomer composition and rubber elasticity. More preferably, it is ⁇ 20 ° C. or lower. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the elastomer composition is used, flexibility and rubber elasticity are hardly exhibited.
  • the Tgb of the acrylic polymer block (b) can be set by setting the monomer weight ratio of each polymer portion according to the Fox formula.
  • the acrylic polymer block (b) has a unit monomer unit (X) having a hydroxyl group
  • the monomer unit (y) is methacrylic from the viewpoint of storage stability and availability.
  • the acid n-butyl is preferred.
  • some of the monomers are monomer units. It may be (y).
  • the block copolymer (A) is usually a polymer of the acid anhydride group and carboxyl group present in the methacrylic polymer block (a) and Z or acrylic polymer block (b). It acts as a reaction point or crosslinking point for quantification or crosslinking.
  • the acid anhydride group and carboxyl group are introduced into the block copolymer in a form in which the acid anhydride group and carboxyl group are protected with an appropriate protective group, or as a precursor of the acid anhydride group and carboxyl group. Thereafter, an acid anhydride group and a carboxyl group can be generated by a known chemical reaction.
  • the content of the acid anhydride group and carboxyl group is determined by the cohesive strength of the acid anhydride group and carboxyl group, the reactivity, the structure and composition of the acrylic block copolymer (A), the acrylic block copolymer (The number of blocks constituting A) varies depending on the glass transition temperature, and the number must be appropriately set as necessary, but is preferably 1.0 or more, more preferably, per block copolymer molecule. 2. Zero or more. This is because if the number is less than 1.0, the heat resistance of the block copolymer due to high molecular weight or crosslinking tends to be insufficient.
  • the glass transition temperature may be adjusted to 130 ° C or lower in order to ensure good melt fluidity. preferable.
  • the acid anhydride group When the composition contains a compound having an active proton, the acid anhydride group easily reacts with a reactive functional group such as an epoxy group.
  • the position of acid anhydride group introduction is particularly limited. In other words, the acid anhydride group may be introduced into the main chain of the methacrylic polymer block (a) or the acrylic polymer block (b), or may be introduced into the side chain.
  • An acid anhydride group is an anhydride group of a carboxyl group, which is a methacrylic polymer block (a) and an acrylic o CH
  • R 3 is hydrogen or a methyl group, two R ° may be the same or different from each other, t is an integer of 0 to 3, and s is an integer of 0 or 1] Contained in the form.
  • t in the general formula (1) is an integer of 0 to 3, preferably 0 or 1, and more preferably 1.
  • t is 4 or more, polymerization tends to be complicated, and cyclization of the acid anhydride group tends to be difficult.
  • R 4 represents hydrogen or a methyl group.
  • R 5 represents hydrogen, a methyl group or a phenyl group. And at least two of the three R 5 groups are selected from a methyl group and a Z or phenyl group, and the three R 5 groups may be the same or different. It is preferable to melt-knead an acrylic block copolymer having at least one unit represented by) and introduce cyclization.
  • the formation of the acid anhydride group is preferably performed by heating the acrylic block copolymer having a precursor of the acid anhydride group at a high temperature at 180 to 300 ° C. It is preferable. When the temperature is lower than 180 ° C, the acid anhydride groups are likely to be insufficiently generated. When the temperature is higher than 300 ° C, the acrylic block copolymer having a precursor of the acid anhydride group itself may be decomposed. is there.
  • the carboxyl group easily reacts with a reactive functional group such as an epoxy group.
  • the introduction position of the carboxyl group is not particularly limited.
  • the carboxyl group may be introduced into the main chain of the methacrylic polymer block ( a ) or the acrylic polymer block (b)! However, it may be introduced into the side chain, but it may be introduced into the main chain for ease of introduction into the methacrylic polymer block (a) and the acrylic polymer block (b). I like it.
  • the monomer having a carboxyl group does not poison the catalyst under the polymerization conditions, it is preferable to introduce the carboxyl group directly by polymerization.
  • the monomer deactivates the catalyst during polymerization it is preferable to carry out by a method of introducing a carboxyl group by functional group conversion.
  • an appropriate carboxyl group is used. It can be introduced into an acrylic block copolymer in a form protected with a protective group or in the form of a functional group that is a precursor of a carboxyl group, and then a functional group can be generated by a known chemical reaction. .
  • acrylic block copolymer (A) having a carboxyl group for example, a precursor of a carboxyl group such as t-butyl (meth) acrylate and trimethylsilyl (meth) acrylate is used.
  • a method of synthesizing an acrylic block copolymer containing a monomer having a functional group to form a carboxyl group by a known chemical reaction such as hydrolysis or acid decomposition (JP 10-298248 A, JP 2001—234146) and general formula (4):
  • R 4 represents hydrogen or a methyl group.
  • R 5 represents hydrogen, a methyl group or a phenol group, and at least two of the three R 5 groups are a methyl group and Z or a phenyl group. selected group forces, the acrylic block copolymer having at least one unit represented by the three R 5 may be the same or different.
  • the unit represented by the general formula (4) is produced by decomposition of an ester unit at a high temperature to form a carboxyl group, and a part of the carboxyl group is cyclized. Utilizing this, the carboxyl group can be introduced by appropriately adjusting the heating temperature and time according to the type and content of the unit represented by the general formula (4).
  • the hydroxyl group of the monomer unit easily reacts with the reactive functional group (d) of the compound (B). This hydroxyl group only needs to act as a reaction point with the compound (B) having a reactive functional group (d).
  • the block copolymer acts as a reaction point or a crosslinking point for high molecular weight or crosslinking. It is preferable to do.
  • the monomer unit (X) having a hydroxyl group has a high temperature while imparting chemical resistance and rubber elasticity to a molded product obtained from the thermoplastic elastomer composition according to the present invention.
  • the general formula (1) In order to maintain the mechanical properties of the general formula (1):
  • R 1 represents hydrogen or a methyl group.
  • p and m are each an integer of 1 or more) in the form of a monomer unit represented by
  • Z or acryl-based polymer block (b) are introduced in an average of 1.0 or more per molecule.
  • the content of the monomer unit) is the reactivity with the compound (B), the structure and composition of the acrylic block copolymer (A), and the block constituting the acrylic block copolymer (A).
  • the number varies depending on the glass transition temperature. It is necessary to set the number appropriately according to need.
  • Force Block copolymer It is 1.0 or more, preferably 2.0 or more per molecule. This is because if the number is less than 1.0, improvement in heat resistance due to high molecular weight or crosslinking of the block copolymer may be insufficient.
  • the method for introducing the monomer unit) into the block copolymer (A) is not particularly limited! However, a (meth) acrylic monomer containing a hydroxyl group is converted into the block copolymer (A).
  • the polymerization may be performed directly at the time of polymerization, or after the block copolymer (A) is polymerized, it may be introduced using an esterification reaction or a transesterification reaction with a diol component. From the viewpoint of easy reaction, a (meth) acrylic monomer containing a hydroxyl group is directly polymerized during the polymerization of the block copolymer (A). It is preferable.
  • (meth) acryl means acrylic or methacryl.
  • Specific (meth) acrylic monomers include (meth) acrylic acid-2-hydroxyethyl,
  • Examples include (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, and the like. These compounds can be used alone or in combination of two or more. Among these, (2-methyoxy) ethyl 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid-4-hydroxyptylca are easy to polymerize and are readily available. From the point of view, it is preferable.
  • the method for producing the acrylic block copolymer (A) is not particularly limited, but it is preferable to use controlled polymerization using an initiator.
  • controlled polymerization include living ion polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization.
  • living radical polymerization power is preferred from the viewpoint of control of molecular weight and structure of acrylic block copolymer.
  • Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss.
  • living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. It is. The definition here is also the latter.
  • Living radical polymerization has been actively researched by various groups in recent years. Examples include those using chain transfer agents such as polysulfide, cobalt borphyrin complex (Journal 'Ob' American 'Chemical' Society, J. Am. Chem. Soc., 1994, Vol. 116, 7943) and -troxide compounds and other radical scavengers (Macromolecules ⁇ 1994, pp. 27, 7228), organic halides and other transition metal complexes as initiators Atom Transfer Radical Polymerization (ATRP) and the like.
  • chain transfer agents such as polysulfide, cobalt borphyrin complex (Journal 'Ob' American 'Chemical' Society, J. Am. Chem. Soc., 1994, Vol. 116, 7943) and -troxide compounds and other radical scavengers (Macromolecules ⁇ 1994, pp. 27, 7228), organic halides and other transition metal complexes as initiators Atom
  • the polymerization method by adjusting the reaction rate and amount of monomers (X) and (y) (for example, the reaction rate of monomers (X) and (y) in the actual reaction system is If they are the same, (y) should be charged more than twice the amount of (X)).
  • the compound (B) constituting the thermoplastic elastomer composition according to the present invention is a polymer having 1.1 or more reactive functional groups (d) in one molecule.
  • Compound (B) improves the molding fluidity as a plasticizer when forming the composition, and at the same time, reacts with an acid anhydride group or carboxyl group in the acrylic block copolymer (A) and a reactive functional group (
  • the acrylic block copolymer (A) is reacted according to d) to have a high molecular weight or to be crosslinked.
  • the number of reactive functional groups (d) represents the average number of reactive functional groups (d) present in the entire compound (B).
  • the reactive functional group (d) in the compound (B) is contained in the compound (B) in an amount of 1.1 or more, preferably 1.5 or more, more preferably 2.0 or more.
  • the number includes the reactivity of the reactive functional group (d), the site and manner in which the reactive functional group (d) is contained, the hydroxyl group and Z or acid anhydride group in the acrylic block copolymer (A) and Varies depending on the number, position and pattern of Z or carboxyl groups.
  • the content of the reactive functional group (d) is less than 1.1, the effect of the block copolymer as a high molecular weight ionic reactant or crosslinking agent is reduced, and the acrylic block copolymer (A ) Tends to be insufficient in improving the heat resistance.
  • the acrylic polymer (B1) is obtained by polymerizing two or more kinds of acrylic monomers, or by polymerizing one or more kinds of acrylic monomers with monomers other than acrylic monomers. Preferably there is.
  • acrylic monomer examples include the acrylic esters and methacrylic esters described in the section of the methacrylic polymer block (a). Of these, the ability to use any one of acrylic acid-n-butyl, ethyl acrylate and 2-methoxyethyl acrylate, or a combination of two or more of these is preferred.
  • the monomer other than the acrylic monomer is not particularly limited as long as it is a monomer copolymerizable with the acrylic monomer.
  • vinyl acetate, styrene and the like can be used.
  • the ratio of the monomer component containing the alitaroyl group to the total monomer components in the acrylic polymer (B1) is preferably 70% by weight or more.
  • the proportion is less than 70% by weight, the weather resistance tends to decrease and the compatibility with the acrylic block copolymer (A) tends to decrease. Moreover, discoloration tends to occur in the molded product.
  • the molecular weight of the acrylic polymer (B1) is not particularly limited, but preferably has a low molecular weight with an average weight molecular weight of 3,000,000 or less S, more preferably 500 to 30, S Particularly preferred is 500 to 10,000.
  • the weight average molecular weight is less than 500, the molded product tends to be sticky.
  • the weight average molecular weight exceeds 30,000, plasticization of the molded product tends to be insufficient.
  • the viscosity of the acrylic polymer (B1) is preferably 35, OOOmPa's or less when measured with a cone-plate type rotational viscometer (E-type viscometer) at 25 ° C. More preferably, it is less than 10, OOOmPa s, and particularly preferably less than 5, OOOmPa's. When the viscosity is higher than 35, OOOmPa's, the plasticizing effect of the composition tends to decrease.
  • the lower limit of the preferred viscosity is not particularly limited, but the normal viscosity of the acrylic polymer is lOmPa's or more
  • the glass transition temperature Tg of the acrylic polymer (B1) is preferably 100 ° C or lower, preferably 25 ° C or lower, as measured by differential scanning calorimetry (DSC). It is particularly preferable that the temperature is 0 ° C or less, more preferably 30 ° C or less. Glass-transition temperature When Tg exceeds 100 ° C, the effect of improving moldability as a plasticizer tends to be insufficient, and the flexibility of the resulting molded product tends to decrease.
  • the acrylic polymer (B1) can be obtained by polymerizing by a known predetermined method.
  • the polymerization method may be appropriately selected according to need, for example, by suspension polymerization, emulsion polymerization, bulk polymerization, living-on polymerization, polymerization using a chain transfer agent, and controlled polymerization such as living radical polymerization.
  • controlled polymerization it is preferable to use controlled polymerization to obtain a polymer having good weather resistance and heat resistance and having a relatively low molecular weight and a small molecular weight distribution, the following method power using high-temperature continuous polymerization is described. More preferable in terms.
  • the acrylic polymer (B1) is preferably obtained by a polymerization reaction at a temperature of 180 to 350 ° C. At this polymerization temperature, an acrylic polymer having a relatively low molecular weight can be obtained without using a polymerization initiator or a chain transfer agent. For this reason, the acrylic polymer is an excellent plasticizer and has good weather resistance.
  • Examples of the reactive functional group (d) include an epoxy group, a carboxyl group, a hydroxyl group, an amino group, and the like, and at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, a hydroxyl group, and an amino group. It is desirable to use it.
  • the epoxy group is selected from the reactivity with the acid anhydride group and carboxyl group contained in the acrylic block copolymer (A) and the introduction of the functional group into the compound (B). Is more preferred.
  • the epoxy group has an average of 1.1 or more, preferably 1 or more per molecule of the compound (B2) having an epoxy group. Preferably, 1.5 or more, more preferably 2.0 or more. The number varies depending on the reactivity of the epoxy group, the site and mode in which the epoxy group is contained, and the content, site and mode of the hydroxyl group per molecule of the acrylic block copolymer (A).
  • Epoxy group When the content of acrylonitrile is less than 1.1, the block copolymer tends to have a high molecular weight or insufficient crosslinking, and the acrylic block copolymer (A) tends to have insufficient heat resistance. .
  • the compound (B2) having an epoxy group is not particularly limited as long as it is a compound having at least one epoxy group in one molecule, and is not limited to bisphenol A type epoxy resin, bisphenol F type epoxy.
  • Resin bisphenol AD type epoxy resin, bisphenol S type epoxy resin, hydrogenated epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin, Novolak type epoxy resin, urethane modified epoxy resin having urethane bond, fluorinated epoxy resin, polybutadiene, rubber modified epoxy resin containing NBR, tetrabromobisphenol A glycidyl ether, etc.
  • Epoxy resin such as epoxy resin, glycidyl ether of polyhydric alcohol and glycidyl ester of polybasic acid
  • Epoxy plasticizers such as epoxidized soybean oil, epoxidized flax oil, and epoxidized fatty acid alkyl esters
  • epoxy group-containing polymers such as Bond First (trade name, manufactured by Sumitomo Chemical Industries); Polymers, epoxy-containing polymers such as ARUFON (trade name, manufactured by Toagosei Co., Ltd.); forces exemplified by styrenic polymers and acrylic polymers, etc. Any epoxy group-containing compound can be used. These epoxy group-containing compounds may be used alone or in combination of two or more.
  • Sarakuko is that the resulting composition is molded at a high temperature, and from the viewpoint of volatility, the compound (B2) having an epoxy group is a styrene polymer or an acrylic polymer. It is a polymer with a weight average molecular weight of 30,000 or less from the viewpoint of more preferable molding fluidity Is preferred. Although there is no particular limitation, for molded products, a low molecular weight strength of 30,000 or less S is preferred ⁇ , 500 to 30,000 strength S is more preferred ⁇ , 500 to 10,000 strength S Particularly preferred. When the weight average molecular weight is less than 500, the molded product tends to be sticky. On the other hand, when the weight average molecular weight exceeds 30,000, plasticization of the molded product becomes insufficient.
  • acrylic polymers are preferred in terms of weather resistance and the like.
  • acrylic polymers include ARUFON (registered trademark) XG4 000, ARUFON UG4000, ARUFON XG4010, ARUFON UG4010, AR UFON XD945, ARUFON XD950, ARUFON UG4030, ARUFON UG 4070, etc. Can be suitably used. These are all acrylics, acrylic polymers such as acrylate / styrene, and contain at least one epoxy group in one molecule.
  • the compound (B2) having an epoxy group is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). More preferably, it is used in the range of 1. parts by weight. If the amount is less than 0.5 parts by weight, the moldability and the heat resistance of the resulting molded product may not be sufficient, and if it exceeds 50 parts by weight, the mechanical properties of the resulting composition will deteriorate. There is a tendency
  • the thermal latent catalyst (C) constituting the thermoplastic elastomer composition according to the present invention is a functional group (c) that is one of a hydroxyl group, an acid anhydride group, and a carboxyl group in the block copolymer (A). ) And the reactive functional group (d) in the compound (B), thereby promoting the cross-linking reaction.
  • the thermal latent catalyst is a catalyst that exhibits higher activity when heated at a predetermined temperature.
  • the functional group (c) and the reactive functional group are used.
  • the group (d) has an effect of suppressing deterioration of moldability by reaction (maintaining good storage stability for a long period of time).
  • the thermal latent catalyst (C) is preferably a compound that exhibits more catalytic activity at a temperature of 60 ° C or higher. If this heat-latent catalyst exhibits catalytic activity at temperatures below 60 ° C, the resulting composition may degrade moldability during storage.
  • thermal latent catalyst (C) examples include (i) a compound obtained by neutralizing a proton acid with an Arrhenius base, (ii) a compound obtained by reacting a proton acid with a Lewis base, (Iii) a compound obtained by reacting a Lewis acid with a Lewis salt group, (iv) a mixture of Lewis acid and trialkyl phosphate, (V) sulfonate esters, (vi) phosphate esters, (vii) -Um compounds, (viii) compounds derived from metal complexes such as aluminum, (ix) quaternary salts, and (X) compounds obtained by reacting a Lewis acid with an araenius base are preferred. Can be mentioned.
  • Examples of the compound (i) obtained by neutralizing a protic acid with an Arenius base include, for example, carboxylic acids, halogenocarboxylic acids, sulfonic acids, sulfuric monoesters, monophosphate and monoester phosphates, polyphosphate esters, boric acid Mono and diesters such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydroxide, zinc, hydroxide, iron, etc.
  • the compound neutralized with a product is mentioned.
  • Examples of the compound (ii) obtained by reacting a protonic acid with a Lewis base include, for example, neurocarboxylic acids, sulfonic acids, sulfate monoesters, phosphate mono- and diesters, polyphosphate esters, borate mono- and diesters , Etc., various amines such as ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethynolamine, diethanolamine, triethanolamine, or trialkylphosphine , Triaryl phosphine, trialkyl phosphite, triaryl phosphite compound, and neicure 2500X, X47—110, 3525, 5225 which are commercially available as acid monobase blocking catalysts (Product name, Kin Guindust Over's Co., Ltd.) and the like.
  • Examples of the compound (iii) obtained by reacting a Lewis acid and a Lewis base include, for example, BF, FeCl,
  • Examples include compounds obtained by reacting Lewis acids such as SnCl, A1C1, and ZnCl with the aforementioned Lewis bases.
  • Examples of the sulfonate esters (V) include those represented by the general formula (5)
  • R 6 is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or an alkyl group
  • R 7 is a sulfonyloxy group via a primary carbon or a secondary carbon. Attached C 3 18 alkyl group, alkenyl group, aryl group, alkaryl group, alkyl group, saturated cycloalkyl group, hydroxycycloalkyl group, unsaturated cycloalkyl group or hydroxycycloalkenyl group. -Group.
  • Such compounds include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nornaphthalenesulfonic acid, and n- Primary alcohols such as propanol, n-butanol, n-xanol and n-octanol or esterified products with secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol, and And ⁇ -hydroxyalkyl sulfonic acid esters obtained by reacting the sulfonic acids with oxysilane group-containing compounds.
  • Examples of the phosphate esters (vi) include compounds represented by the general formula (6). [0126] [Chemical Formula 12]
  • R is an alkyl group having 3 to 10 carbon atoms, a cycloalkyl group or an aryl group, and h is 1 or 2.
  • n-propanol, n-butanol, n-xanol, n-otatano And primary alcohols such as 2-ethylhexanol, and phosphoric monoesters or phosphoric acids of secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol, and cyclohexanol Diesters may be mentioned.
  • examples of the onium compound (vii) include compounds represented by the following general formulas (7) to (10).
  • R 8 , R 10 , R 12 and R 14 in the formula are an alkyl group having 1 to 12 carbon atoms, an alkyl group, an aryl group, an alkaryl group, an alkenol group or a cycloalkyl group.
  • R 8 , R 10 , R 12 and R 14 may be bonded to each other to form a heterocycle having N, P, O or S as a heteroatom
  • R 9 , 1 , R 13 and R 15 Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group, an aryl group, an alkaryl group
  • X— is SbF _, AsF _, PF— or BF "
  • a compound ( vm ) derived from a metal complex such as aluminum can be used.
  • metal complex such as aluminum
  • metal sarcophagus such as aluminum octylate, j8-diketonate aluminum complex, 13 diketoesterate aluminum complex, and o-carbophenolate aluminum complex.
  • ⁇ -diketones used as ligands for the above aluminum complexes include 1,3 diphenylenoles, 1,3 propanediones, 1 phenenoles, 1,3 butane dines, 2, 4 pentane dines, 3 felu rouge 2, 4 pentane dines , 5-dimethyl-2,4 hexanedione, 5 phenyl 2,4 pentanedione, 2,6 dimethyl-3,5 heptanedione, 2,6-tetramethyl-3,5 pentanedione, and the like.
  • Examples of 13 diketoesterol include ethinoreacetoacetate, propinoreacetoacetate, butylacetoacetate, t-butylacetoacetate, ethylbenzoylacetate, and the like.
  • -Lufenol includes 2-hydroxy monobenzaldehyde, 2,1-hydroxyacetophenone, methyl 2-hydroxybenzoate, phenol Examples include 2-hydroxybenzoate.
  • an aluminum complex in which a silanol compound is further mixed with the above metal complex such as aluminum may be used.
  • silanol compounds include triphenylsilanol, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethylether.
  • Toxisilane phenyltriethoxysilane, diphenyljetoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluorodecyltrimethoxysilane , Triphenylmethoxysilane, triphenylethoxysilane and the like.
  • quaternary salt (ix) can also be used as a catalyst. More specifically, tetrabutylammonium chloride such as tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium iodide, tetrabutylammonium halide, tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tetrabutylphosphonium iodide, etc.
  • tetrabutylphosphomum halides such as tetrabutylphosphomum chloride, tetraphenylphosphomum chloride, tetraphenylphosphomum bromide and tetraphenylphosphomum iodide.
  • Examples of the compound (X) obtained by reacting a Lewis acid with an Arenius base include compounds obtained by reacting the above Lewis acid with the above Arenius base.
  • a compound obtained by neutralizing a protonic acid with an Arrhenius base and (ii) a compound obtained by reacting a protonic acid with a Lewis base in view of cost and availability.
  • a compound obtained by reacting a Lewis acid with a Lewis base, and (X) an acid-base reaction compound obtained by reacting a Lewis acid with an Arenius base has a high preferred reaction activity.
  • a compound derived from a metal complex such as aluminum is preferable. From the viewpoint of water resistance and coloring of the molded article finally obtained, (ii) a compound obtained by reacting a protonic acid with a Lewis base is more preferable. . Further, from the viewpoint of suppressing the balance of physical properties of the finally obtained molded body and suppressing the volatile matter from the molded body, a metal salt compound is particularly preferable.
  • the acid-base reaction compound include zinc stearate, calcium stearate, Fatty acid metal salts such as calcium stearate, aluminum stearate, zinc laurate, calcium laurate, magnesium laurate, zinc 2-ethylhexylate, calcium 2-ethylhexylate, magnesium 2-ethylhexylate , Zinc citrate, Sodium citrate, Potassium citrate, Calcium citrate and other metal salts, Sodium benzoate, Zinc benzoate, Aluminum trisbenzoate, Titanium tetrabenzoate, 2-tert-butyl zinc benzoate, 3- Zinc tert-butylbenzoate, Zinc 4-tert-butylbenzoate, Sodium 4-tert-butylbenzoate, Barium 4-tert-butylbenzoate, Barium 2-tert-butylbenzoate, 3-tert- Barium butylbenzoate, barium 4-tert-butylbenzoate, zinc 3,5
  • the fat having 4 to 16 carbon atoms is excellent in the physical properties (secondary workability such as adhesiveness) of the molded product after thermoforming the thermoplastic elastomer of the present invention.
  • a metal salt compound comprising a fatty acid or a benzoic acid derivative compound and zinc is more preferable.
  • Fatty acids having a carbon number of ⁇ 16 include butanoic acid (also known as butyric acid, the same shall apply hereinafter), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid ( Caprylic acid), Nonanoic acid (Pelargonic acid), Decanoic acid (Power Puric acid), Dodecanoic acid (Lauric acid), Tetradecanoic acid (Myristylic acid), Pentadecanoic acid (Pentadecylic acid), Hexadecanoic acid (Palmitic acid) And heptadecanoic acid (margaric acid).
  • butanoic acid also known as butyric acid, the same shall apply hereinafter
  • pentanoic acid valeric acid
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • decanoic acid undecanoic acid, undecanoic acid, and fatty acids having 10 to 17 carbon atoms, such as decanoic acid, undecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadedecanoic acid and heptadecanoic acid are preferred.
  • dodecanoic acid, tridecanoic acid and tetradecanoic acid are more preferred.
  • dodecanoic acid is more preferred in view of the balance of scratch resistance and adhesiveness of the resulting molded article.
  • the benzoic acid derivative compound includes tert-butylbenzoic acid, 3,5-di-tert-butylbenzoic acid, 2,4,6-tri-tert-butylbenzoic acid, 4-tert -Butyl-2,6-dimethylbenzoic acid.
  • the volatility (sublimation) of the catalyst itself bubbles are generated in the molded body during molding when the volatility is high) and molecular weight (when the molecular weight is large, the volatility is low.
  • Tert-Butylbenzoic acid is more preferred because of the balance (which requires more catalyst addition).
  • Examples of diketone compounds having 2 to 16 carbon atoms include 1,2-diketone compounds, 1,3-diketone compounds, 1,4-diketone compounds, 1,5-diketone compounds, and the like. Can be mentioned. Of these, 1,3-diketone compounds are preferred. Examples of 1,3-diketone compounds include acetylylaceton.
  • these thermal latent catalysts (C) can be used alone or in combination of two or more.
  • the blending amount is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the acryl-based block copolymer.
  • the amount of the catalyst is less than 0.01 parts by weight, the catalytic effect tends not to be sufficiently exhibited.
  • the amount exceeds 10 parts by weight, the finally obtained molded product tends to be colored or the water resistance tends to be lowered.
  • the method of adding the thermal latent catalyst (C) is not particularly limited.
  • the thermal latent catalyst (C) is added to the composition containing the acrylic block copolymer (A) and the compound (B) ( Acrylic block copolymer (A), compound (B), and thermal latent catalyst (C) that can be used by coating with C). After kneading A), compound (B) and thermal latent catalyst (C) as an organic solvent solution, the solvent can be removed! ,.
  • thermoplastic elastomer composition of the present invention has a low melt viscosity when molding and excellent melt fluidity (moldability), while it is a block copolymer of an acrylic thermoplastic elastomer composition when heated (A)
  • the cross-linking reaction between the hydroxyl group, acid anhydride group or carboxyl group, which is the functional group (c), and the reactive functional group (d) in the compound) is promoted by using the thermal latent catalyst (C).
  • the thermoplastic elastomer composition may contain a plasticizer for the purpose of improving meltability and improving low temperature characteristics.
  • the plasticizer is preferably used in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the acrylic block copolymer (A). It is more preferable to use within a range. If the blending amount is less than 0.1 part by weight, the meltability and low-temperature property improvement effect of the resulting composition may not be sufficient! In some cases, if it exceeds 50 parts by weight, the mechanical properties of the resulting molded product And heat resistance may deteriorate
  • the plasticizer is not particularly limited, but a plasticizer having an SP value of 8.19.4 is preferable.
  • the SP value is less than 8.0 or more than 9.5, the compatibility between the plasticizer and the acrylic block copolymer (A) is deteriorated, and the physical properties of the resulting molded article are deteriorated. May be played out.
  • plasticizers include dimethyl phthalate, jetyl phthalate, di-n-butyl phthalate, di (2-ethylhexyl) phthalate, diheptyl phthalate, disodecyl phthalate, di-n-phthalate —Phthalic acid derivatives such as octyl, diisonoel phthalate, ditridecyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, and dicyclohexyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; G (2-ethylhexyl) ) Tetrahydrophthalic acid derivatives such as tetrahydrophthalic acid; dimethyl adipate, dibutyl adipate, di-n-xyl adipate, diethyl adipate (2-ethylhexyl), isonoyl adipate, di
  • thermoplastic elastomer composition may be blended in the thermoplastic elastomer composition as necessary in order to reduce the friction of the surface of the obtained molded article.
  • Examples of the lubricant include ester lubricants, polyethylene lubricants, polypropylene lubricants, hydrocarbon lubricants, and silicone oils. Preferred are lubricants.
  • Organic lubricants such as montanic acid wax and stearic acid are not particularly limited. Examples thereof include organic acid amides such as fatty acids and stearic acid amides. These may be used alone or in combination.
  • the polyethylene-based lubricant and the polypropylene-based lubricant mentioned here include an acid-polyethylene lubricant and an acid-polypropylene lubricant, respectively.
  • lubricants include beef tallow 45 hardened oil (melting point 45 ° C; manufactured by Nippon Oil & Fats Co., Ltd., the same shall apply hereinafter), beef tallow 51 hardened oil (melting point 51 ° C), beef tallow 54 Hardened oil (melting point 54 ° C), beef tallow Extremely hardened oil (melting point 60 ° C), LicowaxE (drop point 79-85 ° C; manufactured by Clariant Japan Co., Ltd. I can list them.
  • thermoplastic elastomer compositions and stabilizers are used for the purpose of adjusting the physical properties of the thermoplastic elastomer composition and the resulting molded product.
  • Agents, mold release agents, antibacterial antifungal agents and the like may be further added.
  • examples of the stabilizer include an anti-aging agent, a light stabilizer, and an ultraviolet absorber.
  • a filler may be blended.
  • the filler is not particularly limited, but titanium oxide, carbon black, calcium carbonate, silica, and talc, which are more preferable for inorganic fillers, are more preferable from the viewpoint of improving mechanical properties, reinforcing effect, cost, and the like.
  • thermoplastic elastomer composition ⁇ Method for producing thermoplastic elastomer composition>
  • thermoplastic elastomer composition can be obtained, for example, by using a batch kneader or a continuous kneader. It can also be obtained by dissolving or dispersing in an organic solvent in a tank provided with a stirring blade and then removing the solvent.
  • the batch-type kneading apparatus for example, a mixing roll, a Banbury mixer, a pressure mixer, and a high shear mixer can be used.
  • a continuous kneading apparatus a single screw extruder, a twin screw extruder, a KCK extrusion kneader, or the like can be used.
  • mixing mechanically An existing method such as a method of forming into a pellet can be used.
  • the kneading temperature for producing the thermoplastic elastomer composition is such that the moldability is not lowered by the reaction of the acrylic block copolymer (A) and the compound (B). I prefer temperature.
  • the temperature at which the acrylic block copolymer (A) and the compound (B) react and the moldability deteriorates depends on the type of functional group (c), the amount introduced, the type of coexisting thermal latent catalyst (C), It varies depending on the amount introduced, the composition of the acrylic block copolymer (A) and the compound (B), the compatibility of the acrylic block copolymer (A) and the compound (B), and the like.
  • the temperature during kneading is preferably 200 ° C or less, more preferably 180 ° C or less, so that the composition can be molded. More preferably, the temperature is 150 ° C or lower.
  • the temperature at the time of kneading exceeds 200 ° C, high molecular weight and a crosslinking reaction occur during kneading, and the moldability tends to decrease.
  • the conditions are such that a high molecular weight is partly cross-linked, it may be at a temperature at which molding is possible.
  • an acrylic polymer (B) is added to an acrylic block copolymer solution in which an talyl block copolymer (A) is dissolved in an organic solvent.
  • the thermal latent catalyst (C) and after adding other components as necessary, a method of removing the organic solvent is preferred.
  • the acrylic polymer (B) and the thermal latent catalyst (C) are added to an acrylic block copolymer solution in which the acrylic block copolymer (A) is dissolved in an organic solvent, and then mixed with water. Then, a method of evaporating the organic solvent by heating the mixture as it is, forming droplets of the acrylic block copolymer solution of a predetermined size and heating it is more preferable.
  • thermoplastic elastomer composition When the thermoplastic elastomer composition is pulverized to obtain a powder, an impact type fine pulverizer such as a turbo mill, pin mill, hammer mill, centrifugal mill, etc., shearing with a fixed blade and a rotating blade is used. There is a method using a pulverizer or the like using an action. Furthermore, the pulverization can be performed at room temperature, but it can also be mechanically pulverized using a cooling equipment such as liquid nitrogen. When the thermoplastic elastomer composition is pulverized to obtain a powder, Various powders for preventing mutual adhesion may be adhered to the surface of the composition pellets or the like as a grinding aid.
  • an impact type fine pulverizer such as a turbo mill, pin mill, hammer mill, centrifugal mill, etc., shearing with a fixed blade and a rotating blade is used.
  • pulverization can be performed at room temperature, but it can also be mechanically
  • the grinding aid calcium carbonate, talc, kaolin, silica, fatty acid amide, fatty acid ester, metal sarcophagus and the like can be used. These can be used alone or in combination of two or more.
  • the amount is preferably about 1 to 40 parts by weight per 100 parts by weight of the acrylic block copolymer (A). If it is less than 1 part by weight, the effect is not sufficient, and if it exceeds 40 parts by weight, the mechanical properties of the resulting composition powder may be adversely affected.
  • the particle size of the grinding aid to be used is not particularly limited, but if the particle size is too large, the handling property will be reduced if the particle size is too small and the ability to prevent mutual adhesion.
  • pulverization aid it is preferable to use one having a diameter of 0.5 to 15 / ⁇ ⁇ (measured by a light dispersion method). Although most of the pulverization aid remains in the thermoplastic elastomer composition powder obtained by pulverization, a part of the pulverization aid is detached in the pulverization step and separated in the pulverizer.
  • thermoplastic elastomer composition composition When obtaining a powder from the thermoplastic elastomer composition composition, it is not always necessary to go through a pulverization step.
  • the composition powder when a thermoplastic elastomer composition is obtained by a continuous extruder, the composition powder can be directly obtained as a micropellet by attaching a special die.
  • the compound ( ⁇ ) is dissolved in an acrylic block copolymer solution in which the acrylic block copolymer ( ⁇ ) is dissolved in an organic solvent, and then mixed with water and stirred to obtain a predetermined size.
  • the organic solvent By forming droplets of the acrylic block copolymer solution and heating as it is, the organic solvent is evaporated, and a powder having an appropriate particle size distribution can be obtained.
  • the above-mentioned additives for promoting crosslinking, catalysts, fillers, lubricants, stabilizers, plasticizers, flexibility imparting agents, flame retardants, pigments, antistatic agents, Antibacterial and antifungal agents may be dissolved and dispersed.
  • polybulal alcohol, polybulal alcohol-polyacetic acid copolymer, methylcellulose, or the like may be added as an emulsifying agent.
  • the powder obtained as a result is preferably fractionated only with a particle size of 1 to L000 ⁇ m using a sieve or the like.
  • Powders containing particles smaller than 1 ⁇ m cause agglomeration of the powders, resulting in poor handling and poor powder flow. For this reason, when used for powder slush molding, which will be described later, the powder does not reach the end of the mold sufficiently, and the design of the molded body is impaired. In addition, powders with a particle size larger than 1000 m When used in molding, the powder having a large particle size does not melt sufficiently, so that the design of the molded body is impaired.
  • thermoplastic elastomer composition When the thermoplastic elastomer composition is used for powder slush molding, the above-mentioned method is used to improve the color tone of the molded body and the mold releasability and powder characteristics which are important for slush molding. It is possible to improve the powder characteristics by mixing and dispersing pigments, release agents, anti-blocking powders and the like that are usually used as needed in the powder obtained by .
  • the composition obtained in the section of the method for producing a thermoplastic elastomer can be molded by various methods. For example, it can be applied to powder slush molding, injection molding, injection blow molding, blow molding, extrusion blow molding, extrusion molding, calendar molding, vacuum molding, press molding, etc., but powder slush molding is more preferably used .
  • the powder slush molding is a method in which the composition powder is poured into a molding die heated to a high temperature, melt-molded, and the molded product cooled and solidified is taken out after a certain period of time.
  • the composition needs to flow and be melt-molded even under no pressure, while the molded body after molding is exposed to a usage environment of 100 ° C or higher. For this reason, it is difficult to balance moldability and heat resistance.
  • the composition of the present invention is in an unreacted state of the acrylic block copolymer (A) and the compound (B) before molding, and is excellent in meltability in the mold while being cooled and solidified.
  • the acrylic block copolymer (A) and the compound (B) react within a certain period of time until they are formed, and the acrylic block copolymer (A) is polymerized or crosslinked.
  • the heat resistance of is improved. From this, it can be said that it is a material suitable for powder slush molding.
  • the acrylic block copolymer (A) has a high molecular weight or is cross-linked to improve the heat resistance after molding.
  • the number average molecular weight of the acryl-based block copolymer (A) after molding is 100,000 or more. More preferably, the force S is more than 150,000, more preferably S, more preferably 200,000 or more. When the number average molecular weight is lower than 100,000, the effect of improving heat resistance is lowered. this From such a point, it is preferable that the thermoplastic elastomer composition of the present invention uses an acrylic block copolymer (A) having a number average molecular weight of 40,000 or more.
  • thermoplastic elastomer composition of the present invention is excellent in heat resistance, weather resistance, chemical resistance, oil resistance, adhesion, and flexibility by adjusting the blending and constituent monomer components.
  • Such a composition can be used as a material such as a skin material, a touch panel, or the like that requires good tactile sensation, a material whose appearance is important, an oil resistant material, a vibration damping material, or an adhesive material.
  • the shape may be a sheet, flat plate, film, small molded body, large molded body, or any other shape, and as parts such as panels, handles, grips, and switches. Besides, it can be used as a sealing member.
  • the application is not particularly limited, and examples thereof include automobiles, household electrical appliances, and office electrical appliances.
  • automotive skin materials automotive tactile materials, automotive exterior materials, automotive panels, automotive handles, automotive grips, automotive switches, and household or office electrical panel
  • household appliances or office appliance switches for example, household appliances or office appliance switches.
  • it is suitably used for an automobile interior skin.
  • BA, EA, HEA, HBA, AA, and MMA are n-butyl acrylate, ethyl acrylate, 2-hydroxybutyrate, acrylate-4-hydroxybutyl, acrylic acid, methacrylic, respectively. Represents methyl acid.
  • the molecular weight, the conversion rate of the polymerization reaction, and the evaluation of each physical property described in the examples were performed according to the following methods.
  • the molecular weight shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using black mouth form as the mobile phase.
  • a GPC system manufactured by Waters was used, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK was used for the column.
  • Shodex K-804 polystyrene gel manufactured by Showa Denko KK was used for the column.
  • the conversion rate of the polymerization reaction shown in this example was measured using the following analyzer and conditions.
  • Equipment used Gas chromatography GC-14B manufactured by Shimadzu Corporation
  • Sample preparation The sample was diluted about 10 times with ethyl acetate, and butyl acetate or acetonitrile was used as an internal standard.
  • the ethanol resistance shown in the examples and comparative examples was measured under the following conditions.
  • the textured sheet produced in the examples and comparative examples was placed on a flat surface, and a drop of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped onto the pipette and left at room temperature for 24 hours. Thereafter, the surface was observed and visually evaluated as ⁇ for those with no trace and X for those with whitening observed.
  • ethanol manufactured by Wako Pure Chemical Industries, Ltd.
  • the textured sheet produced in the examples and comparative examples was placed on a flat surface, and one drop of liquid paraffin strength light tester Co., Ltd. was dropped with a pipette and left at room temperature for 24 hours. Thereafter, the liquid paraffin was wiped off with Kimwipe (registered trademark) (manufactured by Cressia Co., Ltd.), the surface was observed, and visually, the one with no trace was evaluated as ⁇ , and the one with whitening was evaluated as X.
  • Kimwipe registered trademark
  • a 5 cm ⁇ 5 cm sample was cut from the sheet obtained by molding and left in an oven at 130 ° C. for 24 hours. Changes in the textured surface were compared before and after the test, and evaluated according to the following criteria. Surface gloss changes before and after the test.
  • a 5 cm ⁇ 5 cm sample was cut from the sheet obtained by molding and left in a 110 ° C. oven for 24 hours. Changes in the textured surface were compared with a dull meter (Nippon Denshoku Industries Co., Ltd., VG2000, angle set to 60 ° C) and evaluated according to the following criteria.
  • Dalos change is 0.5 to 0.7: ⁇
  • the heat resistance shown in the examples and comparative examples was measured under the following conditions.
  • a 2 cm ⁇ 10 cm skin material sample was cut from the sheet obtained by molding and cured at room temperature for 24 hours. After that, it was set on a urethane foam mold (140 mm long x 200 mm wide x 10 mm high lid, made of SUS304) with the embossed surface facing down. Stir the polyisocyanate (CEI-264, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 34 g of polyol (manufactured by Sanyo Chemical Industry Co., Ltd., HC-150) for 10 seconds at room temperature using a non-mix mixer. After pouring into the set urethane foam, it was covered and allowed to foam for 10 minutes.
  • a urethane foam mold 140 mm long x 200 mm wide x 10 mm high lid, made of SUS304
  • the composition was press-molded to prepare a skin material.
  • Cartridge type polyurethane made by Air Tight Co., Ltd.
  • main component is 4,4'-diphenylmethane diisocyanate
  • melt fluidity (powder slash property) of the resin at the time of molding shown in the examples and comparative examples was evaluated by the following method.
  • a mass of the composition was prepared.
  • a lump of the composition was put into a small pulverizer SK-M2 (manufactured by Kyoritsu Riko Co., Ltd.) cooled with dry ice, and pulverized while adding dry ice.
  • the obtained powder was evaluated under the following conditions.
  • the obtained powder was spread thinly on a leather metal plate heated to 200 ° C, and the molten state was visually observed.
  • Evaluation index Powder that melts completely: Yes, Powder that has some residue
  • Formability was evaluated by performing slush molding using a 29.4 cm X 20.4 cm flat plate with a texture (mold for slush molding) and a box slush molding machine such as a powder box.
  • the condition is that 2 kg of the thermoplastic elastomer composition powder is charged, the slush molding die heated to 280 ° C is set in a slush molding machine, and then the mold is heated to 260 ° C. After turning, it was held for 6 seconds and then reversed. After 60 seconds, the mold was cooled with cooling water for 40 seconds. Furthermore, air cooling was performed, and when the sheet temperature reached 30 ° C, the sheet was peeled off from the mold to obtain a molded sheet (thickness: 1. Omm).
  • the moldability of the obtained molded sheet was evaluated as follows.
  • a part of the back side of the molded sheet has a residue of the thermoplastic elastomer composition powder at the time of molding, and irregularities are observed;
  • thermoplastic elastomer composition powder is not sufficiently melted on the back side of the molded sheet, and the front side of the back side of the molded sheet is uneven; ⁇ Abrasion evaluation test>
  • a 3 cm x 10 cm sample was cut out from the sheet obtained by slush molding, and a wear test was performed with a wear tester.
  • Haydon-type wear tester 14DR manufactured by Shinto Kagaku Co., Ltd.
  • the test was conducted, visually observed, and evaluated according to the following criteria.
  • Cutter Tungsten carbide, 4.8 mm square x 19 mm length, cutting edge radius 12.7 mm
  • Cutter orientation Cutter length and surface mounted with the cutter blade side down (see Fig. 1) .
  • the test was performed with a load of 1N, visually observed, and evaluated according to the following criteria.
  • MFR melt flowability
  • Evaluation index A case where the powder slash property was good after 6 days was evaluated as ⁇ , and a case where the powder slash property after 6 days was bad was evaluated as X.
  • an acrylic block copolymer In order to obtain an acrylic block copolymer, the following operation was performed. Introduction of force ruboxyl groups into the polymer was carried out with reference to WO2003Z068836. After replacing the inside of the pressure-resistant reactor with nitrogen, 0.89 parts by weight of copper bromide, 100 parts by weight of n-butyl acrylate, and 4.46 parts by weight of acrylic acid-t-butyl were charged, and stirring was started. Then, 2,5-diethyl acetate dibromoadipate as an initiator 1. Acetonitrile (nitrogen published) 24 parts by weight 9. A solution prepared by dissolving 18 parts by weight was added, and the temperature was raised to 75 ° C. Stir for minutes. When the solution temperature reached 75 ° C., 0.11 part by weight of pentamethylethylenetriamine was added as a ligand to initiate polymerization of the acrylic polymer block.
  • n -butyl acrylate and t-butyl acrylate were determined by gas chromatography analysis of the sampling solution at regular intervals from the start of polymerization. During polymerization, The polymerization rate was controlled by adding n-methylethylenetriamine as needed. Pentamethyljetylenetriamine was added twice in total (0.21 part by weight in total) during the acrylic polymer block polymerization.
  • Toluene was added to the reaction solution containing the acrylic block copolymer to make the polymer concentration 25% by weight. To 100 parts by weight of this solution, 0.41 part by weight of p-toluenesulfonic acid was added, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C. for 3 hours.
  • reaction solution was sampled to confirm that the solution became colorless and transparent! /, And 0.50 part by weight of Radiolite # 3000 manufactured by Showa Chemical Industry was added as a filter aid. Thereafter, the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid content was separated using a pressure filter equipped with a polyester felt as a filter medium.
  • the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, the solid content was separated using the pressure filter shown above equipped with a polyester felt as a filter medium, and an acrylic block copolymer having a carboxyl group was separated. A polymer solution containing the coalescence was obtained.
  • polymer 1 This polymer solution was vacuum-dried at 80 ° C to obtain an acrylate block copolymer having a carboxyl group (hereinafter referred to as "polymer 1").
  • the glass transition temperature of the methacrylic polymer block (a) of the polymer 1 obtained in Production Example 1 was calculated according to the above Fox formula, and was loe.
  • a pressure stirrer is charged with 200 parts by weight of pure water and 0.7% by weight of polybulal alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name KH-17) (23.3 parts by weight as a 3% aqueous solution).
  • polybulal alcohol manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name KH-17
  • Example 1 400 parts by weight of polymer solution obtained in Example 1 (solid content concentration 25% by weight), 10 parts by weight of ARUFON (registered trademark) UG4010 (manufactured by Toagosei Co., Ltd.) which is an acrylic polymer having an epoxy group RS700 (polyester ester plasticizer, manufactured by Asahi Denki Kogyo Co., Ltd.) 10 parts by weight, extremely hardened beef tallow oil (melting point 60 ° C: manufactured by Nippon Oil & Fats Co., Ltd.) 1 part by weight ,Power 0.3 parts by weight of a black powder pigment based on one bon black was added.
  • ARUFON registered trademark
  • UG4010 manufactured by Toagosei Co., Ltd.
  • RS700 polymer having an epoxy group RS700 (polyester ester plasticizer, manufactured by Asahi Denki Kogyo Co., Ltd.) 10 parts by weight, extremely hardened beef tallow oil (melting point 60 ° C: manufactured
  • this dispersion was heated to 90 ° C, held at 90 ° C for 5 minutes, and then cooled to obtain a polymer slurry in which latex adhered to the surface of the polymer particles as an antiblocking agent. Obtained.
  • This slurry was dehydrated with a batch centrifugal filter and dried with a batch fluid dryer at a maximum temperature of 50 ° C. to obtain a polymer powder having a moisture content of 0.4%.
  • MMA-b- (BA-co-HEA) —b— MMA-type acrylic block copolymer-2 (in this case, (BA—co—HEA) means a polymer block consisting of BA and HEA. — B- (BA-co-HEA) —b— MMA consists of MMA blocks and (BA—co—HEA) It means a block copolymer in which blocks are bonded in the above order. (Hereinafter referred to as “Polymer 2”)
  • the conversion rate of MMA was determined in the same manner as in the acrylic polymer block polymerization. Sampling was performed at the time when MMA was added, and the conversion rate of MMA was determined based on this. During polymerization, the polymerization rate was controlled by adding pentamethylgerylenetriamine as needed. Pentamethyljetylene triamine was added a total of 3 times (total 5.2 g) during block polymerization of the methacrylic polymer. When the conversion rate of MMA was 61.7%, 1300 g of toluene was added, and the reaction was terminated by cooling the reactor in a water bath.
  • Kiyo Ward 500SH manufactured by Kyowa Chemical Co., Ltd.
  • Kiyo Ward 500SH manufactured by Kyowa Chemical Co., Ltd.
  • the adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution.
  • This solution was dried to remove the solvent and residual monomer, and the intended polymer 1 was obtained.
  • the average number of hydroxyl groups per molecule is 40 (calculated from the charged amount).
  • the number average molecular weight Mn was 106,000, and the molecular weight distribution MwZMn was 1.61.
  • (MMA-co-EA) means a polymer block composed of MMA and EA).
  • Polymer 3 the following operation was performed.
  • the conversion rate of MMA was determined in the same manner as in the acrylic polymer block polymerization. Sampling was performed when MMA was added, and the conversion rate of MMA was determined based on this sampling. . During polymerization, the polymerization rate was controlled by adding pentamethylgerylenetriamine as needed. Pentamethyljetylenetriamine was added a total of 6 times (total 3.9 g) during block polymerization of the methacrylic polymer. When the MMA conversion rate was 94.4%, 1030 g of toluene was added, and the reactor was cooled in a water bath to complete the reaction.
  • Kiyoward 500SH manufactured by Kyowa Chemical Co., Ltd.
  • the adsorbent was filtered with a Kiriyama funnel to obtain a colorless and transparent polymer solution. This solution was dried to remove the solvent and residual monomer, and the intended polymer 2 was obtained.
  • the average number of hydroxyl groups per molecule is 10 (calculated from the charged amount).
  • the number average molecular weight Mn was 74, 110, and the molecular weight distribution MwZMn was 1.53.
  • the conversion rate of MMA was determined in the same manner as in the acrylic polymer block polymerization. Sampling was performed at the time when MMA was added, and the conversion rate of MMA was determined based on this. During polymerization, the polymerization rate was controlled by adding pentamethylgerylenetriamine as needed. Pentamethyljetylene triamine was added a total of 6 times (3.7 g in total) during block polymerization of the methacrylic polymer. When the conversion rate of MMA was 95.1%, 2000 g of toluene was added, and the reaction was terminated by cooling the reactor in a water bath.
  • the conversion rate of MMA was determined in the same manner as in the acrylic polymer block polymerization. Sampling was performed at the time when MMA was added, and the conversion rate of MMA was determined based on this. During polymerization, the polymerization rate was controlled by adding pentamethylgerylenetriamine as needed. Pentamethyljetylene triamine was added twice in total (1.5 g in total) during the methacrylic polymer block polymerization. When the conversion power of MMA was 1 ⁇ 20.6%, 1300 g of toluene was added, and the reactor was cooled in a water bath to complete the reaction.
  • the number average molecular weight Mn was 77,400, and the molecular weight distribution MwZMn was 1.44. Toluene was added to the resulting reaction solution to adjust the polymer concentration to 25% by weight.
  • Kiyoward 500SH and 9,275 g as a solid base were purged with nitrogen, and the mixture was stirred at 30 ° C for 1 hour.
  • the solution was sampled and the reaction was completed after confirming that the solution was neutral.
  • the reactor was pressurized to 0.1 to 0.4 MPaG with nitrogen, and the solid content was separated using a pressure filter equipped with a polyester felt as a filter medium (filtration area 0.45 m 2 ) to obtain a polymer solution. It was.
  • the solvent component was evaporated from the polymer solution.
  • S CP100 heat transfer area lm 2
  • Evaporation of the polymer solution was performed by setting the heating medium oil at the evaporator inlet to 180 ° C, the evaporator vacuum to 90 Torr, the screw rotation speed to 60 rpm, and the polymer solution feed rate to 32 kgZh.
  • the polymer is made into a strand with a ⁇ 4mm die through a discharger, cooled in a water tank filled with 3% suspension of Alflow H50ES (main component: ethylene bis stearamide, manufactured by Nippon Oil & Fats Co., Ltd.), A cylindrical pellet was obtained with a pelletizer. In this way, polymer 6 pellets were produced.
  • the average number of carboxyl groups per molecule is about 10 (calculated from the charged amount).
  • ARUFON registered trader
  • the obtained sample was heat-pressed using a leather metal plate at a set temperature of 200 ° C for 8 minutes (compression molding machine NSF-50, manufactured by Kondo Metal Industry Co., Ltd.) and evaluated for lmm thickness A molded product for use was obtained. The transferability of the texture pattern by press molding was good. Table 1 shows the evaluation results of scratch resistance and heat resistance of the obtained sheet.
  • a press-molded sheet was obtained in the same manner as in Example 1 except that zinc stearate was not added.
  • the transferability of the texture pattern by press molding was good.
  • Table 1 shows the evaluation results of scratch resistance and heat resistance of the obtained sheet.
  • Powder B-1 obtained in Production Example 3 1 part by weight of zinc stearate (manufactured by NOF Co., Ltd., GF-200) was added to 100 parts by weight in a node blend, and powder C — Got one. Using the obtained powder C-1, evaluation of slush moldability (performed by moldability) and evaluation of molded sheet characteristics obtained thereby were performed. Table 2 shows the evaluation results.
  • Powder B-1 obtained in Production Example 3 To 100 parts by weight, 0.1 part by weight of zinc stearate (manufactured by Nippon Oil & Fats Co., Ltd., GF200) was added in a node blend, and powder C — Got two. Obtained Using the powder C-2, slush moldability was evaluated (performed by moldability>) and the molded sheet characteristics obtained thereby were evaluated. Table 2 shows the evaluation results.
  • Powder B—obtained in Production Example 3 100 parts by weight of zinc laurate (Nippon Yushi Co., Ltd., Zinclaurate GP) 0.085 parts by weight was added in a non-blend, Powder C-3 was obtained. Using the obtained powder C-3, evaluation of slush moldability (performed by moldability) and evaluation of molded sheet characteristics obtained thereby were performed. Table 2 shows the evaluation results. From the catalog, 0.085 parts by weight of zinc laurate in this example and 0.1 parts by weight of zinc stearate shown in Example 3 have substantially the same zinc content.
  • Powder B—obtained in Production Example 3 100 parts by weight of bis (acetylacetonato) zinc (Tokyo Chemical Industry Co., Ltd., reagent) 0.044 parts by weight in a node blend To obtain powder C-4. Using the obtained powder C-4, slush moldability was evaluated (performed by moldability>) and molded sheet characteristics obtained thereby were evaluated. Table 2 shows the evaluation results. From the catalog, 0.044 parts by weight of bis (acetylacetonato) zinc in this example and 0.1 parts by weight of zinc stearate shown in Example 3 have substantially the same zinc content.
  • Powder B-3 was obtained in the same manner as in Production Example 3 except for adding 3 parts by weight. Using the obtained powder B-3, slush moldability evaluation (implemented according to moldability>) and molded sheet characteristics obtained thereby were evaluated. The evaluation results are shown in Table 2.
  • Example 4 The adhesion of the molded sheets obtained in Example 4, Example 5 and Example 7 was evaluated by the urethane adhesion test 1>. The evaluation of V and deviation was ⁇ .
  • thermoplastic elastomer composition that is effective in the present invention has good moldability, and the obtained molded sheet has good heat resistance in addition to wear resistance and scratch resistance, and is used as a skin material. It can be seen that the material is excellent in balance.
  • urethane foam is often used as a base material, but it can be seen that urethane foam also has good adhesion.
  • Polymer 2 obtained in Production Example 4 100 parts by weight (40 g) of all acrylics with 1.1 or more epoxy groups per molecule (approximate value 4 (from catalog)) ARUFON UG4010 (manufactured by Toagosei Co., Ltd.), a polymer based, set to 100 ° C at a rate of 10 parts by weight Using a Laboplast mill 50C150 (blade shape: roller type R60, Toyo Seiki Seisakusho Co., Ltd.), melt-kneading was performed at lOOrpm for 15 minutes to obtain a lump sample. The storage stability (Evaluation Method 1) was evaluated using the obtained bulk sample. The results are shown in Table 3.
  • Reference Example 3 From Table 3 (Reference Examples 1 to 3), in Reference Example 3, a polymer having an epoxy group was blended using lab plastomiles, and the reaction proceeded from that point and was already in progress before storage at 80 ° C. Melt fluidity is poor, and when it is stored at 80 ° C, it does not melt completely.
  • Reference Example 1 and Reference Example 2 are samples using a polymer having a hydroxyl group instead of a polymer having a carboxyl group, and thus it can be seen that the storage stability is improved.
  • the sample using the polymer 2 having a sterically protected hydroxyl group in Reference Example 1 is particularly excellent in melt fluidity and storage stability.
  • Polymer 3 obtained in Production Example 5 100 parts by weight (35g) of all acrylics and acrylic containing 1.1 or more epoxy groups per molecule (approximate value 4 (from catalog)) 10 parts by weight of ARUFON UG4010 (manufactured by Toagosei Co., Ltd.) and 2.6 parts by weight of zinc acetate (anhydrous) (manufactured by Wako Pure Chemical Industries, Ltd.) were set at 100 ° C. Labo Plast Mill 50C15 Using 0 (blade shape: roller type R60, Toyo Seiki Seisakusho Co., Ltd.), melt-kneading was performed at lOOrpm for 15 minutes to obtain a lump sample.
  • the obtained sample was heat-pressed using a leather metal plate at a set temperature of 200 ° C for 8 minutes (compression molding machine NSF-50, manufactured by Kondo Metal Industry Co., Ltd.), and the leather texture was transferred.
  • a molded product for evaluation having a thickness of 1 mm was obtained.
  • These molded bodies were subjected to ethanol resistance, oil resistance, urethane adhesion, and heat resistance tests.
  • a powder slush property test was performed on the powder obtained by pulverizing the lump sample obtained above, thereby confirming the melt fluidity at the time of molding.
  • the storage stability (evaluation method-2) was evaluated using the obtained powder. The results are shown in Table 4.
  • Polymer 6 obtained in Production Example 8 100 parts by weight (35 g) of all acrylics and acrylic containing 1.1 or more epoxy groups per molecule (approximate value 4 (from catalog)) ARUFON UG4010 (manufactured by Toagosei Co., Ltd.), a polymer based on Laboplast Mill 50C150 (blade shape: roller type R60 Toyo Seiki Manufacturing Co., Ltd.) set to 100 ° C at a ratio of 10 parts by weight The mixture was melt-kneaded at lOOrpm for 15 minutes to obtain a lump sample. Evaluation was carried out in the same manner as in Example 9 using the obtained sample. The results are shown in Table 4.
  • Example 9 Example 1 0 Comparative Example 1 Polymer 3 100
  • thermoplastic elastomer composition for powder slush molding using a polymer 3 having a hydroxyl group that is three-dimensionally protected It can be seen that not only the slush moldability and storage stability are excellent, but the resulting molded article is also excellent in heat resistance, ethanol resistance and oil resistance. Furthermore, when the obtained sheet is used as an automobile skin material, it is generally necessary to adhere the sheet to polyurethane or the like used as a base material, but the composition according to the present invention is good. It shows that it shows adhesiveness.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulding By Coating Moulds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition élastomère thermoplastique présentant d'excellentes propriétés en matière de stabilité en stockage et de fluidité à l'état fondu lors du moulage. Une pièce moulée obtenue à partir de cette composition élastomère thermoplastique présente d'excellentes propriétés en termes de résistance à la chaleur, de résistance aux huiles, de résistance chimique, d'adhésivité et de flexibilité. L'invention concerne plus spécifiquement une composition élastomère thermoplastique contenant un copolymère à blocs acrylique (A) dont la masse moléculaire moyenne, telle que déterminée par chromatographie par perméation sur gel, est comprise entre 30 000 et 200 000, un composé (B) comportant au moins 1,1 groupes fonctionnels réactifs (d) dans une molécule et un catalyseur thermique latent (C). Le copolymère à blocs acrylique (A) est constitué de 10 à 60 % en poids d'un bloc polymère méthacrylique (a), essentiellement constitué d'un monomère méthacrylique et présentant une température de transition vitreuse de 25 à 130 °C, et de 90 à 40 % en poids d'un bloc polymère acrylique (b). Ledit copolymère à blocs acrylique (A) contient au moins un groupe fonctionnel (c), choisi dans le groupe constitué d'un groupe hydroxyle, d'un groupe anhydride d'acide et d'un groupe carboxyle, et se situant au moins dans le bloc polymère (a) ou le bloc polymère (b).
PCT/JP2007/062181 2006-06-21 2007-06-15 Composition élastomère thermoplastique Ceased WO2007148636A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007039535A1 (de) * 2007-08-21 2009-02-26 Evonik Röhm Gmbh Verfahren zur Herstellung von Pentablockcopolymeren mit OH-funktionalisierten Blöcken auf (Meth)acrylatbasis
JP2018184544A (ja) * 2017-04-26 2018-11-22 アロン化成株式会社 熱可塑性エラストマー組成物
JP2018184541A (ja) * 2017-04-26 2018-11-22 アロン化成株式会社 熱可塑性エラストマー組成物

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JP2006104410A (ja) * 2004-10-08 2006-04-20 Kaneka Corp 熱可塑性エラストマー組成物およびそれを用いた成形品
JP2006104419A (ja) * 2004-10-08 2006-04-20 Kaneka Corp 熱可塑性エラストマー組成物およびそれを用いた成形品
JP2006124588A (ja) * 2004-10-29 2006-05-18 Kaneka Corp 熱可塑性エラストマー組成物および成形品
JP2006249173A (ja) * 2005-03-09 2006-09-21 Kaneka Corp 熱可塑性エラストマー組成物およびそれを用いた成形品
JP2007182482A (ja) * 2006-01-05 2007-07-19 Kaneka Corp 熱可塑性エラストマー組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006104410A (ja) * 2004-10-08 2006-04-20 Kaneka Corp 熱可塑性エラストマー組成物およびそれを用いた成形品
JP2006104419A (ja) * 2004-10-08 2006-04-20 Kaneka Corp 熱可塑性エラストマー組成物およびそれを用いた成形品
JP2006124588A (ja) * 2004-10-29 2006-05-18 Kaneka Corp 熱可塑性エラストマー組成物および成形品
JP2006249173A (ja) * 2005-03-09 2006-09-21 Kaneka Corp 熱可塑性エラストマー組成物およびそれを用いた成形品
JP2007182482A (ja) * 2006-01-05 2007-07-19 Kaneka Corp 熱可塑性エラストマー組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007039535A1 (de) * 2007-08-21 2009-02-26 Evonik Röhm Gmbh Verfahren zur Herstellung von Pentablockcopolymeren mit OH-funktionalisierten Blöcken auf (Meth)acrylatbasis
JP2018184544A (ja) * 2017-04-26 2018-11-22 アロン化成株式会社 熱可塑性エラストマー組成物
JP2018184541A (ja) * 2017-04-26 2018-11-22 アロン化成株式会社 熱可塑性エラストマー組成物

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