JP2007167973A - Suction pad using thermoplastic elastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a recyclable suction pad using thermoplastic elastomer, having excellent sucking property, not causing any deformation of a sucked material. <P>SOLUTION: This suction pad includes: a cylindrical base and a skirt-like sucking part connected to one end of the base. The sucking part is made of thermoplastic elastomer composition containing thermoplastic elastomer, and the thermoplastic elastomer contains a hydrogen bonding crosslink part having a carbonyl contained base and covalent bonding crosslink part and/or nitrogen-containing heterocycle in side chains. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a suction pad using a thermoplastic elastomer.

Conventionally, a suction pad connected to a vacuum generation source is used to transport an object to be adsorbed in a factory or the like. As the material of the portion of the suction pad that comes into contact with the object to be adsorbed (hereinafter referred to as “adsorption portion”), rubbers such as NBR, silicon rubber, urethane rubber, and fluorine rubber are usually used.
In recent years, for the purpose of making the suction pad recyclable and the like, it has been studied to use a thermoplastic elastomer for the suction portion. For example, an adsorption pad using an olefinic thermoplastic elastomer has been proposed.

However, a suction pad using a conventional thermoplastic elastomer is inferior in adsorptivity and sometimes causes deformation of an object to be adsorbed.
Therefore, an object of the present invention is to provide a suction pad that is recyclable and has excellent adsorptivity and does not cause deformation of an object to be adsorbed.

  As a result of diligent research, the present inventor has found that by using a specific thermoplastic elastomer, an adsorbent pad that has excellent recyclability, excellent adsorbability, and does not cause deformation of an adsorbed object can be obtained. Completed the invention.

That is, the present invention provides the following (1) to (8).
(1) A suction pad comprising a cylindrical base portion and a skirt-like suction portion connected to one end of the base portion,
The adsorbing part is composed of a thermoplastic elastomer composition containing a thermoplastic elastomer,
The adsorption pad in which the thermoplastic elastomer contains a hydrogen-bonding cross-linking site having a carbonyl-containing group, a covalent cross-linking site and / or a nitrogen-containing heterocycle in the side chain.
(2) The suction pad according to (1), wherein the thermoplastic elastomer composition further contains a styrene thermoplastic elastomer having a weight average molecular weight of 100,000 or more and a plasticizer.
(3) The adsorption pad according to (1) or (2), wherein the thermoplastic elastomer composition further contains an ethylene propylene copolymer having a polypropylene block and an ethylene propylene block.
(4) The above thermoplastic elastomer can be crosslinked by at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes, and thioethers at the covalently crosslinked sites. The suction pad according to any one of 1) to (3).
(5) The adsorption pad according to any one of (1) to (4), wherein the side chain containing the hydrogen-bonding cross-linked site contains a structure represented by the following formula (1).

(In the formula, A is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom, or these An organic group that may contain atoms or groups.)
(6) The above-mentioned (1) to (1), wherein the side chain containing the hydrogen-bonding crosslinking site contains a structure represented by the following formula (2) or (3) bonded to the main chain at the α-position or β-position. The suction pad according to any one of (5).

(Wherein A is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)) or Sulfur atom or organic group optionally containing these atoms or groups.)
(7) The suction pad according to any one of (1) to (6), wherein the covalently crosslinked site contains a structure represented by the following formula (4A).

(In the formula, R is a single bond, an oxygen atom or a sulfur atom, or an organic group which may contain these atoms or groups.)
(8) The adsorption pad according to (7), wherein the covalently crosslinked site contains a structure represented by the following formula (7A) that binds to the main chain at the α-position or β-position.

(In the formula, R is a single bond, an oxygen atom or a sulfur atom, or an organic group which may contain these atoms or groups.)

  The suction pad of the present invention is excellent in recyclability, excellent in adsorptivity, and does not cause deformation of the object to be adsorbed.

The present invention is described in detail below.
The suction pad of the present invention is a suction pad comprising a cylindrical base portion and a skirt-like suction portion connected to one end of the base portion,
The adsorbing part is composed of a thermoplastic elastomer composition containing a thermoplastic elastomer,
The thermoplastic elastomer is an adsorption pad containing a hydrogen-bonding cross-linked site having a carbonyl-containing group, a covalent bond cross-linked site and / or a nitrogen-containing heterocycle in the side chain.

FIG. 1 is a schematic view showing an example of the suction pad of the present invention. 1A is a perspective view, FIG. 1B is a front view, and FIG. 1C is an end view taken along the line IC-IC in FIG.
The suction pad 10 shown in FIG. 1 includes a cylindrical base portion 12 and a skirt-like suction portion 14 connected to one end of the base portion 12.
The base portion 12 has a cylindrical shape, and the suction portion 14 is connected to one end thereof and has an opening at the other end. In use, the base 12 is connected to a vacuum source at this opening.
The suction part 14 has a skirt shape and is connected to one end of the base part 12. The opening end of the adsorption portion 14 (the end portion not connected to the base end 12) is in close contact with the object to be adsorbed during use.

In FIG. 1, the base 12 is cylindrical and the suction portion 14 is bellows. However, the suction pad of the present invention is not limited to the shape shown in FIG. In addition, various members other than the base portion and the adsorption portion may be provided.
In addition, the dimension in FIG. 1 is a dimension of the suction pad used in the Example mentioned later, and does not limit the dimension of the suction pad of this invention.

  In this invention, an adsorption | suction part consists of a thermoplastic elastomer composition containing a specific thermoplastic elastomer. Hereinafter, the thermoplastic elastomer composition will be described in detail.

The thermoplastic elastomer used in the thermoplastic elastomer composition contains a hydrogen-bonding cross-linked site having a carbonyl-containing group, a covalent bond cross-linked site and / or a nitrogen-containing heterocycle in the side chain.
The reason why the thermoplastic elastomer composition retains excellent recyclability and is excellent in mechanical strength is not clear, but the thermoplastic elastomer has a hydrogen-bonding crosslinking site having a carbonyl-containing group in the side chain, and By containing a covalently bonded crosslinking site and / or nitrogen-containing heterocycle, in addition to hydrogen bonding (interaction) by a carbonyl-containing group, covalent bonding and / or hydrogen bonding by a nitrogen-containing heterocyclic ring at the covalent crosslinking site It is thought that this is because of the formation.

  The hydrogen-bonding crosslinking site having a carbonyl-containing group is introduced as a chemically stable bond (that is, a covalent bond) to an atom (usually a carbon atom) that forms the main chain of the elastomeric polymer. In addition, the covalent cross-linking site and / or the nitrogen-containing heterocycle is introduced as a chemically stable bond (that is, a covalent bond) to an atom (usually a carbon atom) that forms the main chain of the elastomeric polymer. Yes.

The main chain of the thermoplastic elastomer is an elastomeric polymer. The elastomeric polymer is not particularly limited as long as it is a polymer that exhibits rubber-like elasticity at room temperature (that is, an elastomer), but its glass transition point is preferably 25 ° C. or lower. As the elastomeric polymer, for example, conventionally known natural polymers and synthetic polymers can be used.
Specifically, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber. (CR), diene rubbers such as butyl rubber (IIR), ethylene-propylene-diene rubber (EPDM) and hydrogenated products thereof; ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM) ), Olefin-based rubbers such as chlorosulfonated polyethylene, acrylic rubber, fluorine rubber, polyethylene rubber, and polypropylene rubber; epichlorohydrin rubber; polysulfide rubber; silicone rubber; and urethane rubber.

  The elastomeric polymer may be an elastomeric polymer containing a resin component, and specific examples thereof may be a hydrogenated polystyrene elastomeric polymer (for example, SBS, SIS, SEBS), polyolefin. Based elastomeric polymer, polyvinyl chloride based elastomeric polymer, polyurethane based elastomeric polymer, polyester based elastomeric polymer, and polyamide based elastomeric polymer.

Further, the elastomeric polymer may be liquid or solid, and the molecular weight thereof is not particularly limited. For example, diene rubbers such as isoprene rubber and butadiene rubber have a weight average molecular weight of 100,000 to 1,500. Is preferably 1,000,000, more preferably 300,000 to 1,000,000.
In this invention, a weight average molecular weight is a weight average molecular weight (polystyrene conversion) measured by the gel permeation chromatography (Gel Permeation Chromatography (GPC)). For the measurement, tetrahydrofuran (THF) is preferably used as a solvent.

In the present invention, two or more of the above elastomeric polymers can be mixed and used. In this case, the mixing ratio of the respective elastomeric polymers can be set to any ratio depending on the use of the suction pad, the required physical properties, and the like.
Further, as described above, the glass transition point of the elastomeric polymer is preferably 25 ° C. or less, and when the elastomeric polymer has two or more glass transition points, or two or more elastomeric polymers are mixed. When used, at least one of the glass transition points is preferably 25 ° C. or lower. When the glass transition point of the elastomeric polymer is within this range, the adsorbing portion made of the thermoplastic elastomer composition exhibits rubber-like elasticity at room temperature, which is preferable.
In the present invention, the glass transition point is a glass transition point measured by differential scanning calorimetry (DSC-Differential Scanning Calorimetry). In measuring the glass transition point, the rate of temperature rise is preferably 10 ° C./min.

  Such elastomeric polymers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), Diene rubbers such as butyl rubber (IIR); olefin rubbers such as ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), and ethylene-butene rubber (EBM) have a glass transition point of 25 ° C. or less. In addition, the adsorbing part made of the thermoplastic elastomer composition obtained is preferable because it exhibits rubber-like elasticity at room temperature. In addition, when an olefin rubber is used, the tensile strength when the resulting thermoplastic elastomer composition is crosslinked is improved, and deterioration of the composition is suppressed because there is no double bond.

In the present invention, the amount of bound styrene of the styrene-butadiene rubber (SBR), the hydrogenation rate of the hydrogenated elastomeric polymer, etc. are not particularly limited, and can be in any range depending on the use of the adsorption pad, the required physical properties, etc. Can be adjusted.
When ethylene-propylene-diene rubber (EPDM), ethylene-acrylic rubber (AEM), ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM) is used as the main chain of the elastomeric polymer, its ethylene content Is preferably 10 to 90 mol%, more preferably 40 to 90 mol%. It is preferable for the ethylene content to be in this range because it is excellent in compression set resistance, mechanical strength, and particularly tensile strength when a thermoplastic elastomer (composition) is obtained.

The thermoplastic elastomer contains a hydrogen-bonding crosslinking site having a carbonyl-containing group, a covalent bonding site and / or a nitrogen-containing heterocycle in the side chain of the above-mentioned elastomeric polymer.
The hydrogen-bonding cross-linking site is not particularly limited as long as it has a carbonyl-containing group, but it is one of preferred embodiments that further has a nitrogen-containing heterocycle.
The carbonyl-containing group is not particularly limited as long as it contains a carbonyl group, and specific examples thereof include amide, ester, imide, carboxy group, and carbonyl group. The compound into which such a group can be introduced is not particularly limited, and specific examples thereof include ketones, carboxylic acids and derivatives thereof.
Examples of the carboxylic acid include organic acids having a saturated or unsaturated hydrocarbon group. The hydrocarbon group may be aliphatic, alicyclic or aromatic. Examples of the carboxylic acid derivative include carboxylic acid anhydrides, thiocarboxylic acids (mercapto group-containing carboxylic acids), esters, ketones, amino acids, amides, imides, dicarboxylic acids, and monoesters thereof.

Specific examples of the carboxylic acid and derivatives thereof include malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, p-hydroxybenzoic acid, p -Carboxylic acids such as aminobenzoic acid and mercaptoacetic acid and those carboxylic acids containing substituents; carboxylic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride, etc. Products: aliphatic esters such as maleic acid ester, malonic acid ester, succinic acid ester, glutaric acid ester, ethyl acetate; phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-p-hydroxy Aromatic esters such as benzoate; quinone, anthraquinone Ketones such as naphthoquinone; amino acids such as glycine, tyrosine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N- (p-aminobenzoyl) -β-alanine; Maleamide, maleamic acid (maleic monoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N, N'-hexamethylenebis (acetamide), malonamide, cycloserine, 4-acetamidophenol, p- Amides such as acetamide benzoic acid; imides such as maleimide and succinimide.
Among these, cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride are preferable, and maleic anhydride is more preferable.

The nitrogen-containing heterocycle is not particularly limited as long as it contains a nitrogen atom in the heterocycle. Those having a hetero atom other than a nitrogen atom in the heterocyclic ring, for example, a sulfur atom, an oxygen atom, a phosphorus atom and the like can also be used. Since the thermoplastic elastomer used in the present invention has a heterocyclic structure, hydrogen bonds forming crosslinks are strengthened, and the resulting thermoplastic elastomer composition is excellent in tensile strength.
The nitrogen-containing heterocycle may have a substituent. Specific examples of the substituent include alkyl groups such as methyl group, ethyl group, (iso) propyl group, and hexyl group; methoxy group Alkoxy groups such as ethoxy group, (iso) propoxy group; groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; cyano group; amino group; aromatic hydrocarbon group; ester group; ether group Acyl group; thioether group and the like, and combinations thereof can also be used. The substitution position of these substituents is not particularly limited, and the number of substituents is not limited.
Further, the nitrogen-containing heterocycle may or may not have aromaticity, but if it has aromaticity, the resulting thermoplastic elastomer composition has higher tensile strength. It is preferable because the mechanical strength is further improved.

The nitrogen-containing heterocycle is preferably a 5-membered ring or a 6-membered ring.
Specific examples of such nitrogen-containing heterocycle include pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β -Isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, imidazoline, imidazolone, imidazolidone Hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, in , Indoline, carbazole, phenothiazine, indolenine, isoindole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine, pyrazine, Phenazine, tetrazine, benzoxazole, benzisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine, histidine, triazolidine, Melamine, adenine, guanine, thymine, cytosine and their induction The body is mentioned. Among these, the nitrogen-containing 5-membered ring is preferably exemplified by the following compounds, triazole derivatives represented by the following formula (10) and imidazole derivatives represented by the following formula (11). These may have the above-described various substituents, and may have hydrogen atoms added or eliminated.

In the formula, each of the substituents X, Y and Z independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an amino group. . In the above formula (10), at least one of X and Y is not a hydrogen atom, and in the above formula (11), at least one of X, Y and Z is not a hydrogen atom.
Examples of such substituents X, Y, and Z include, in addition to hydrogen atoms and amino groups, specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, dodecyl group, stearyl Linear alkyl group such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 2- Examples include branched alkyl groups such as ethylhexyl group; aralkyl groups such as benzyl group and phenethyl group; and aryl groups such as phenyl group, tolyl group (o-, m- or p-), dimethylphenyl group and mesityl group.
Among these, an alkyl group, in particular, a butyl group, an octyl group, a dodecyl group, an isopropyl group, and a 2-ethylhexyl group is preferable because the processability of the resulting thermoplastic elastomer composition becomes good.

  Moreover, about a nitrogen-containing 6-membered ring, the following compound is illustrated preferably. These may also have the above-described various substituents, and may be those to which a hydrogen atom has been added or eliminated.

  Moreover, what condensed the said nitrogen-containing heterocycle and the benzene ring or the said nitrogen-containing heterocycle can also be used, and the following condensed rings are specifically illustrated suitably. These condensed rings may also have the above-described various substituents, and may have hydrogen atoms added or eliminated.

  Among such nitrogen-containing heterocycles, the triazole ring, pyridine ring, thiadiazole ring, imidazole ring and hydantoin ring are the recyclability, compression set resistance, hardness and mechanical strength of the resulting thermoplastic elastomer composition. In particular, it is preferable because of excellent tensile strength.

  When the hydrogen-bonding cross-linked site has a nitrogen-containing heterocycle, the carbonyl-containing group and the nitrogen-containing heterocycle may be introduced to the main chain by mutually independent side chains. The nitrogen heterocycle is preferably introduced into the main chain by one side chain, and more preferably introduced into the main chain by one side chain represented by the following formula (1).

  In the formula, A is a nitrogen-containing heterocycle, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a sulfur atom, or these atoms Or it is the organic group which may contain the group.

Here, the nitrogen-containing heterocyclic ring A specifically includes the nitrogen-containing heterocyclic rings exemplified above.
Specific examples of the substituent B include, for example, a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a sulfur atom, or those described later. An organic group is mentioned.
Examples of the alkyl group having 1 to 10 carbon atoms of the amino group NR ′ include, for example, isomers, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, A decyl group is mentioned.
As the organic group, for example, an alkylene group having 1 to 20 carbon atoms or an aralkylene group which may contain these atoms or groups; an alkylene ether group having 1 to 20 carbon atoms having these atoms or groups as terminals (An alkyleneoxy group such as —O—CH ₂ CH ₂ — group), an alkyleneamino group (such as —NH—CH ₂ CH ₂ — group), an alkylene thioether group (an alkylene thio group such as —S—CH ₂ CH ₂ -group), aralkylene ether group (aralkyleneoxy group), aralkylene amino group or aralkylene thioether group.

The oxygen atom, sulfur atom and amino group NR ′ of the substituent B and the oxygen atom, amino group NR ′ and sulfur atom in the organic group terminated with these atoms or groups are combined with the adjacent carbonyl group to form a conjugate. It is preferable to form an ester group, an amide group, an imide group, a thioester group, or the like.
Among these, the substituent B is an oxygen atom, a sulfur atom or an amino group forming a conjugated system; an alkylene ether group having 1 to 20 carbon atoms, an alkyleneamino group or an alkylenethioether having these atoms or groups at the terminal Group, an amino group (NH), an alkyleneamino group (—NH—CH ₂ — group, —NH—CH ₂ CH ₂ — group, —NH—CH ₂ CH ₂ CH ₂ — group), alkylene ether More preferably, it is a group (—O—CH ₂ — group, —O—CH ₂ CH ₂ — group, —O—CH ₂ CH ₂ CH ₂ — group).

  The carbonyl-containing group and the nitrogen-containing heterocycle are introduced into the polymer main chain at the α-position or β-position as one side chain represented by the following formula (2) or (3). preferable.

  In the formula, A is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or sulfur. An atom or an organic group which may contain these atoms or groups.

Here, the nitrogen-containing heterocyclic ring A is basically the same as the nitrogen-containing heterocyclic ring A of the above formula (1), and the substituents B and D are each independently of the substituent B of the above formula (1). The same as above.
However, the substituent D in the said Formula (3) is C1-C20 which may contain a single bond; an oxygen atom, a nitrogen atom, or a sulfur atom among what was illustrated by the substituent B of the said Formula (1). It is preferable to form a conjugated system of an alkylene group or an aralkylene group, and more preferably a single bond. That is, it is preferable to form an alkyleneamino group or an aralkyleneamino group having 1 to 20 carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom together with the imide nitrogen of the above formula (3). More preferably, the nitrogen-containing heterocycle is directly bonded to the imide nitrogen of 3). Specifically, the substituent D is a single bond; an alkylene ether having 1 to 20 carbon atoms or an aralkylene ether group which may contain an oxygen atom, a sulfur atom or an amino group as described above; an isomer; Methylene group, ethylene group, propylene group, butylene group, hexylene group, phenylene group, xylylene group, and the like.

  The ratio of the carbonyl-containing group and the nitrogen-containing heterocycle of the thermoplastic elastomer is not particularly limited, and is complementary to 2: 1 (1: 1 in the case of the imide structure of the above formula (3)). This is preferable because it is easy to form an interaction and can be easily manufactured.

The side chain containing such a hydrogen-bonding cross-linked site is preferably introduced at a ratio (introduction ratio) of 0.1 to 50 mol% with respect to 100 mol% of the main chain portion, and 0.3 More preferably, it is introduced at a ratio of ˜30 mol%.
If it is less than 0.1 mol%, the tensile strength at the time of crosslinking may not be sufficient, and if it exceeds 50 mol%, the crosslinking density may increase and rubber elasticity may be lost. That is, when the introduction rate is within the above-described range, cross-linking is efficiently formed between molecules due to the interaction between the side chains of the thermoplastic elastomer, so that the tensile strength at the time of cross-linking is high and the recyclability is excellent. Therefore, it is preferable.
When the carbonyl-containing group and the nitrogen-containing heterocycle are independently introduced, the introduction ratio may be considered as a set of both groups according to the ratio of the carbonyl-containing group and the nitrogen-containing heterocycle. When such a group is excessive, the larger group may be considered as a reference.
Further, the introduction ratio is such that, for example, when the main chain portion is ethylene-propylene rubber (EPM), the monomer having the side chain portion introduced per 100 units of ethylene and propylene monomer units is 0.1-50. About unit.

The covalent cross-linking site includes a “compound that generates a covalent bond” and a functional group capable of generating at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane, and thioether. This is a site that has been cross-linked by reaction.
In the present invention, examples of the “compound that forms a covalent bond” include, for example, two or more amino groups and / or imino groups in one molecule (in the case where both amino groups and imino groups are present, these groups are added together). Polyamine compound having 2 or more); polyol compound having 2 or more hydroxy groups in one molecule; polyisocyanate compound having 2 or more isocyanate (NCO) groups in one molecule; thiol group (mercapto group) in one molecule And a polythiol compound having two or more.

  Examples of the polyamine compound include the following alicyclic amines, aliphatic polyamines, aromatic polyamines, and nitrogen-containing heterocyclic amines.

  Specific examples of the alicyclic amine include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, and di- (aminomethyl). ) Cyclohexane.

  Specific examples of the aliphatic polyamine include, for example, methylenediamine, ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3-diaminopentane, hexamethylenediamine, diaminoheptane, diaminododecane, diethylenetriamine, diethylaminopropylamine. N-aminoethylpiperazine, triethylenetetramine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3-propanediamine, N , N′-diethyl-1,3-propanediamine, N, N′-diisopropyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N, N′-diethyl-1, 6-Hexanediamine N, N ', N "- trimethylbis (hexamethylene) include triamines.

  Specific examples of aromatic polyamines and nitrogen-containing heterocyclic amines include diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tris (dimethylaminomethyl) phenol, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3-amino-1,2,4-triazole is mentioned.

  In the polyamine compound, one or more of its hydrogen atoms may be substituted with an alkyl group, an alkylene group, an aralkylene group, an oxy group, an acyl group, a halogen atom, or the like. And may contain a heteroatom such as.

  A polyamine compound may be used individually by 1 type, or may be used together 2 or more types. The mixing ratio when two or more kinds are used in combination can be adjusted to an arbitrary ratio according to the use of the suction pad, the required physical properties, and the like.

  Among the polyamine compounds exemplified above, hexamethylenediamine, N, N′-dimethyl-1,6-hexanediamine, diaminodiphenylsulfone, etc. are highly effective in improving compression set resistance, mechanical strength, particularly tensile strength. preferable.

  As long as the polyol compound is a compound having two or more hydroxy groups, its molecular weight and skeleton are not particularly limited, and examples thereof include the following polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. .

  Specific examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3- At least one selected from polyhydric alcohols such as butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, pentaerythritol, ethylene oxide, propylene oxide, butylene Polyols obtained by adding at least one selected from oxides, styrene oxides and the like; polyoxytetramethylene glycol and the like may be mentioned, and these may be used alone or in combination of two or more.

  Specific examples of the polyester polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. Or a condensation polymer of two or more with one or more of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid and other low molecular carboxylic acids and oligomeric acids Ring-opening polymers such as propionlactone and valerolactone, and the like may be used alone or in combination of two or more.

  Specific examples of other polyols include, for example, polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, Hexanediol, polyethylene glycol laurylamine (for example, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (for example, N, N-bis (2-methyl-2-hydroxyethyl) laurylamine) Polyethylene glycol octylamine (for example, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octyl Amines (eg, N, N-bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (eg, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine ( Examples thereof include low molecular polyols such as N, N-bis (2-methyl-2-hydroxyethyl) stearylamine), and these may be used alone or in combination of two or more.

Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4 ' -MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1 , 5-Naphthalene diisocyanate (NDI) aromatic polyisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate ( BDI), such as aliphatic polyisocyanates, trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated MDI), H ₆ TDI (hydrogenated TDI) Diisocyanate compounds such as cycloaliphatic polyisocyanates; polyisocyanate compounds such as polymethylene polyphenylene polyisocyanates; carbodiimide-modified polyisocyanates of these isocyanate compounds; isocyanurate-modified polyisocyanates of these isocyanate compounds; The urethane prepolymer obtained by making it react with the polyol compound illustrated by (1) is mentioned, These may be used individually by 1 type, or may be used together 2 or more types.

  As long as the polythiol compound is a compound having two or more thiol groups, its molecular weight and skeleton are not particularly limited. Specific examples thereof include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, , 9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, toluene-3,4-dithiol, 3,6-dichloro-1, 2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol, 1 3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4'-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6- Dioxaoctane, 1,5-dimercapto-3-thiapentane, 1,3,5-triazine-2,4,6-trithiol (trimercapto-triazine), 2-di-n-butylamino-4,6-dimercapto -S-triazine, trimethylolpropane tris (β-thiopropionate), trimethylolpropane tris (thioglycolate), polythiol (thiocol or thiol-modified polymer (resin, rubber, etc.)). One species may be used alone, or two or more species may be used in combination.

  As a functional group capable of generating at least one bond selected from the group consisting of amides, esters, lactones, urethanes, ethers, thiourethanes and thioethers by reacting with such “compounds that form a covalent bond” And a cyclic acid anhydride group, a hydroxy group, an amino group, a carboxy group, an isocyanate group, a thiol group, and the like.

The above-mentioned “compound that forms a covalent bond” reacts with the functional group capable of generating at least one bond selected from the group consisting of the amide, ester, lactone, urethane, ether, thiourethane, and thioether described above. Crosslinks form a covalent crosslink site.
The thermoplastic elastomer has at least one covalently crosslinked site per molecule, and in particular, crosslinked by at least one bond selected from the group consisting of lactone, urethane, ether, thiourethane and thioether. Is preferably 2 or more, more preferably 2 to 20, and still more preferably 2 to 10.
In the present invention, this covalently crosslinked site contains a tertiary amino group (-N =), which means that the resulting thermoplastic elastomer composition has compression set resistance and mechanical strength (in particular, This is preferable because the elongation at break and the strength at break are further improved. This is considered to be due to the tertiary amino group interacting with the carbonyl-containing group and the nitrogen-containing heterocyclic ring through hydrogen bonds, thereby further improving the crosslinking density. Therefore, as the “compound that generates a covalent bond”, among those exemplified above, polyethylene glycol laurylamine (eg, N, N-bis (2-hydroxyethyl) laurylamine), polypropylene glycol laurylamine (eg, N , N-bis (2-methyl-2-hydroxyethyl) laurylamine), polyethylene glycol octylamine (eg, N, N-bis (2-hydroxyethyl) octylamine), polypropylene glycol octylamine (eg, N, N -Bis (2-methyl-2-hydroxyethyl) octylamine), polyethylene glycol stearylamine (for example, N, N-bis (2-hydroxyethyl) stearylamine), polypropylene glycol stearylamine (for example, N, N- Scan is preferably (2-methyl-2-hydroxyethyl) stearylamine).

  In the present invention, the covalently crosslinked site preferably contains at least one structure represented by any one of the following formulas (4) to (6), and G in the formula is More preferably, it contains a tertiary amino group.

  In the formula, E, J, K and L are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), a sulfur atom or these atoms. Or it is the organic group which may contain the group, G is the C1-C20 hydrocarbon group which may contain the oxygen atom, the sulfur atom, or the nitrogen atom, and may be branched.

Here, the substituents E, J, K, and L are each independently the same as the substituent B of the above formula (1).
Specific examples of the substituent G include, for example, methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1 Alkylene groups such as 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group, 1,10-decylene group, 1,11-undecylene group, 1,12-dodecylene group; N, N-diethyl Dodecylamine-2,2'-diyl, N, N-dipropyldodecylamine-2,2'-diyl, N, N-diethyloctylamine-2,2'-diyl, N, N-dipropyloctylamine- 2,2'-diyl, N, N-diethylstearylamine-2,2'-diyl, N, N-dipropylstearylamine-2,2'-diyl; vinylene group; 1,4-cyclohexylene group Bivalent Cyclic hydrocarbon group; divalent aromatic hydrocarbon group such as 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,3-phenylenebis (methylene) group; propane- Trivalent hydrocarbon groups such as 1,2,3-triyl, butane-1,3,4-triyl, trimethylamine-1,1 ′, 1 ″ -triyl, triethylamine-2,2 ′, 2 ″ -triyl; And tetravalent hydrocarbon groups represented by the following formulas (12) and (13); and substituents formed by combining them.

  Among these, it is one of the preferred embodiments that contains the structure represented by the above formula (4A). In the above formula (4A), R is a single bond, an oxygen atom or a sulfur atom, or an organic group that may contain these atoms or groups.

  Furthermore, in the present invention, the covalently crosslinked site is a structure represented by any one of the following formulas (7) to (9) bonded to the main chain of the elastomeric polymer described above at the α-position or β-position. It is preferable to contain at least one, and it is more preferable that G in the formula contains a tertiary amino group. Specific examples of the structure represented by any one of the following formulas (7) to (9) include compounds represented by the following formulas (14) to (25).

  Here, the substituents E, J, K and L are each independently the same as the substituents E, J, K and L in the above formulas (4) to (6), and the substituent G is This is basically the same as the substituent G in the above formula (4).

（式中、ｌは、１以上の整数を表す。）

(In the formula, l represents an integer of 1 or more.)

（式中、ｌ、ｍおよびｎは、それぞれ独立に１以上の整数を表す。）

(In the formula, l, m and n each independently represents an integer of 1 or more.)

  Moreover, it is one of the preferable aspects to contain the structure represented by the said Formula (7A) couple | bonded with the principal chain of the said elastomeric polymer mentioned above by alpha-position or beta-position. In the above formula (7A), R is a single bond, an oxygen atom or a sulfur atom, or an organic group that may contain these atoms or groups.

  In the present invention, it is preferable that the covalent cross-linking site is formed by a reaction between a cyclic acid anhydride group and a hydroxy group or an amino group and / or an imino group.

  The thermoplastic elastomer contains, in the side chain, a hydrogen bondable cross-linking site having the above-mentioned carbonyl-containing group and the above-described covalent bond cross-linking site. The covalent bond crosslinking site and the hydrogen bond crosslinking site may be contained in the same side chain or in different side chains.

  The thermoplastic elastomer preferably has a glass transition point of 25 ° C. or lower. When the thermoplastic elastomer has two or more glass transition points, or when two or more thermoplastic elastomers are used in combination, it is preferable that at least one of the glass transition points is 25 ° C. or lower. When the glass transition point is 25 ° C. or lower, the adsorbing portion exhibits rubber-like elasticity at room temperature.

  The production method for obtaining the thermoplastic elastomer is not particularly limited, and an ordinary method can be selected. Specifically, a nitrogen-containing heterocyclic ring is added to the elastomeric polymer containing a cyclic acid anhydride group in the side chain. A reaction step (hereinafter referred to as “reaction step A”) for reacting a compound capable of introducing a hydrogen atom, followed by a reaction step (hereinafter referred to as “reaction step B”) for reacting a compound that forms a covalent bond; A nitrogen-containing heterocycle may be introduced after a reaction step (hereinafter referred to as “reaction step C”) in which a compound that forms a covalent bond is reacted with an elastomeric polymer containing a cyclic acid anhydride group in the side chain. A method of performing a reaction step (hereinafter referred to as “reaction step D”) in which a compound is reacted is preferably exemplified.

In the reaction step A, a compound capable of introducing a nitrogen-containing heterocyclic ring and an elastomeric polymer containing a cyclic acid anhydride group in the side chain are mixed, and the compound capable of introducing a nitrogen-containing heterocyclic ring and the cyclic acid anhydride are mixed. This is a step of reacting at a temperature at which the group can chemically bond (for example, 80 to 200 ° C.) to open the cyclic acid anhydride group. By this reaction, the side chain of the obtained thermoplastic elastomer contains the structure represented by the above formula (2) or (3).
In the reaction step A, the compound capable of introducing a nitrogen-containing heterocyclic ring is reacted with a part of the cyclic acid anhydride group of the elastomeric polymer containing a cyclic acid anhydride group in the side chain. Is preferable from the viewpoint that the cyclic acid anhydride group becomes a covalent cross-linking site. The part is preferably 1 mol% or more, more preferably 30 mol% or more, and further preferably 50 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, the effect of introducing a nitrogen-containing heterocycle is exhibited, and the recyclability is further enhanced.

Here, the “elastomeric polymer containing a cyclic acid anhydride group in the side chain” means that the cyclic acid anhydride group is introduced into the atom forming the main chain by a chemically stable bond (that is, a covalent bond). It is obtained by reacting the elastomeric polymer with a compound capable of introducing a cyclic acid anhydride group.
Specific examples of the compound capable of introducing a cyclic acid anhydride group include cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, and derivatives thereof.

The elastomeric polymer containing a cyclic acid anhydride group in the side chain is obtained by graft polymerization of a cyclic acid anhydride to a conventional method, for example, the above-mentioned elastomeric polymer under normal conditions such as stirring under heating. It may be produced by a method of making it available, or a commercially available product may be used.
Examples of commercially available products include maleic anhydride-modified isoprene rubbers such as LIR-403 (manufactured by Kuraray Co., Ltd.) and LIR-410A (Kuraray Co., Ltd.); modified isoprene rubbers such as LIR-410 (manufactured by Kuraray Co., Ltd.); Clinac 110 , 221 and 231 (manufactured by Policer), etc .; carboxy-modified polybutenes such as CPIB (manufactured by Nisseki Chemical Co., Ltd.), HRPIB (manufactured by Nisseki Chemical Co., Ltd.); Nucrel (manufactured by DuPont Mitsui Polychemical) , Maleic anhydride-modified ethylene-propylene rubber such as Yucaron (manufactured by Mitsubishi Chemical Corporation), Tuffmer M (for example, MA8510 (manufactured by Mitsui Chemicals)); Acid-modified ethylene-butene rubber; Adtex series (maleic anhydride-modified EVA, anhydrous Inacid-modified EMA (manufactured by Nippon Polyolefin Co., Ltd.), HPR series (maleic anhydride-modified EEA, maleic anhydride-modified EVA (manufactured by Mitsui / Jupon Polyolefin)), Bond Fast series (maleic anhydride-modified EMA (manufactured by Sumitomo Chemical Co., Ltd.)) )), Dumiran series (maleic anhydride modified EVOH (manufactured by Takeda Pharmaceutical Co., Ltd.)), Bondine (ethylene / acrylic ester / maleic anhydride terpolymer (manufactured by Atofina)), Tuftec (maleic anhydride modified) SEBS, M1943 (manufactured by Asahi Kasei)), Kraton (maleic anhydride modified SEBS, FG1901X (manufactured by Kraton Polymer)), tufprene (maleic anhydride modified SBS, 912 (manufactured by Asahi Kasei)), Septon (maleic anhydride modified SEPS) (Kuraray)), Lexpearl (nothing Maleic anhydride-modified polyethylene such as maleic acid-modified EVA, ET-182G, 224M, 234M (manufactured by Nippon Polyolefin Co., Ltd.), Aurorene (maleic anhydride-modified EVA, 200S, 250S (manufactured by Nippon Paper Chemicals)); Admer ( Examples thereof include maleic anhydride-modified polypropylene such as QB550 and LF128 (Mitsui Chemicals).

  The compound capable of introducing a nitrogen-containing heterocyclic ring may be the nitrogen-containing heterocyclic ring itself exemplified above, or a substituent that reacts with a cyclic acid anhydride group such as maleic anhydride (for example, a hydroxy group, a thiol group). And a nitrogen-containing heterocyclic ring having an amino group).

In the reaction step B, the reaction product obtained in the reaction step A and a compound that forms a covalent bond are mixed, and a temperature at which the compound can be covalently bonded to the covalently crosslinked site in the thermoplastic elastomer (for example, 80 ˜200 ° C.). By this reaction, crosslinks represented by the above formulas (7) to (9) are formed.
In the reaction step B, the compound that generates a covalent bond is the same as that in the reaction product obtained in the reaction step A so that the number of crosslinks due to the covalent bond is an appropriate number (for example, 1 to 3 per molecule). What is necessary is just to make it react with a covalent bond bridge | crosslinking site | part.

In the reaction step C, a compound that forms a covalent bond and an elastomeric polymer that contains a cyclic acid anhydride group in the side chain are mixed, and the compound that forms a covalent bond and the cyclic acid anhydride group are covalently bonded. It is a step of causing the cyclic acid anhydride group to ring-open by reacting at a temperature (for example, 80 to 200 ° C.). By this reaction, structures represented by the above formulas (7) to (9) are formed.
In the above reaction step C, the compound that forms a covalent bond contains a cyclic acid anhydride group in the side chain so that the number of crosslinks by the covalent bond is an appropriate number (for example, 1 to 3 per molecule). What is necessary is just to make it react with the cyclic acid anhydride group in the elastomeric polymer to do.

In the reaction step D, the elastomeric polymer obtained in the reaction step C is mixed with a compound capable of introducing a nitrogen-containing heterocyclic ring, and the cyclic acid anhydride group remaining in the elastomeric polymer and the compound are chemically bonded. It is a step of reacting at a temperature (for example, 80 to 200 ° C.) to open a cyclic acid anhydride group. By this reaction, a structure represented by the above formula (2) or (3) is formed.
In the reaction step D, the compound capable of introducing a nitrogen-containing heterocycle is reacted with part or all of the cyclic acid anhydride group remaining in the elastomeric polymer obtained in the reaction step C. A cyclic acid anhydride group is preferred from the viewpoint of becoming a covalently linked cross-linking site. The part is preferably 1 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol% or more with respect to 100 mol% of the cyclic acid anhydride group. Within this range, the effect of introducing a nitrogen-containing heterocyclic ring is exhibited, and the tensile strength at the time of crosslinking is further increased.

  In the above production method, each group (structure) of the side chain of the thermoplastic elastomer, that is, an unreacted cyclic acid anhydride group, represented by the above formulas (2), (3) and (7) to (9). The structure to be confirmed can be confirmed by commonly used analytical means such as NMR and IR spectrum.

The bonding position of the nitrogen-containing heterocyclic ring in the thermoplastic elastomer will be described. For convenience, the nitrogen-containing heterocycle is referred to as “nitrogen-containing n-membered ring compound (n ≧ 3)”.
The bonding positions described below ("1 to n positions") are based on the IUPAC nomenclature. For example, in the case of a compound having three nitrogen atoms having an unshared electron pair, the bonding position is determined by the order based on the IUPAC nomenclature. Specifically, the bonding positions are indicated on the 5-membered, 6-membered and condensed nitrogen-containing heterocycles exemplified above.
In the thermoplastic elastomer, the bonding position of the nitrogen-containing n-membered ring compound bonded to the copolymer directly or via an organic group is not particularly limited, and may be any bonding position (position 1 to position n). Preferably, it is the 1-position or 3-position to n-position.

When the nitrogen-containing n-membered ring compound contains one nitrogen atom (for example, a pyridine ring), a chelate is easily formed in the molecule, and the composition has excellent physical properties such as tensile strength. The (n-1) position is preferred.
By selecting the bonding position of the nitrogen-containing n-membered ring compound, the thermoplastic elastomer is easy to form crosslinks due to hydrogen bonding, ionic bonding, coordination bonding, etc. between the thermoplastic elastomer molecules, and is excellent in recyclability. Excellent mechanical properties, especially tensile strength.

  The thermoplastic elastomer composition contains one or more thermoplastic elastomers. The mixing ratio in the case of containing two or more kinds can be set to any ratio depending on the use of the suction pad, the required physical properties, and the like.

In the present invention, it is one of preferred embodiments that the thermoplastic elastomer composition further contains a styrene-based thermoplastic elastomer having a weight average molecular weight of 100,000 or more and a plasticizer.
In this embodiment, recyclability is good, and physical properties such as mechanical strength and compression set resistance are excellent. This is because the styrenic thermoplastic elastomer is incompatible, has low fluidity, forms an independent phase, and the styrenic thermoplastic elastomer has a high affinity with oil. This is presumably because the oil is taken into the crosslinked structure of the thermoplastic elastomer while the styrene-based thermoplastic elastomer has absorbed the oil.
In addition, in the present invention, compression set resistance is improved for the same reason even when a polyolefin resin such as polypropylene (PP) or ethylene-propylene-diene rubber (EPDM) is used. Since the thermoplastic elastomer is used, the degree of improvement in compression set resistance is improved and mechanical strength is also improved as compared with the case of using these resins.
In particular, the use of a thermoplastic elastomer having a side chain containing a secondary amino group and a carbonyl-containing group as the thermoplastic elastomer increases the tensile strength at the time of crosslinking and further improves compression set resistance. For reasons, it is preferable to use a thermoplastic elastomer having a side chain containing a secondary amino group, a nitrogen-containing heterocyclic ring and a carbonyl-containing group, resulting in higher tensile strength at the time of crosslinking and further improved compression set resistance. It is more preferable because the mechanical strength such as tensile strength is further improved while maintaining the properties to be achieved.

The styrenic thermoplastic elastomer is a styrenic thermoplastic elastomer obtained as a block copolymer from an aromatic vinyl compound and a conjugated diene, and has a terminal block polymerization portion with an aromatic vinyl corresponding to a crosslinking point at the end. There is no particular limitation as long as the weight average molecular weight is 100,000 or more.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and the like, and these may be used alone or in combination of two or more. May be.
Specific examples of the conjugated diene include butadiene, isoprene and a mixture thereof.

In the present invention, the method for producing the styrenic thermoplastic elastomer is not particularly limited. For example, the polymer (block (A)) obtained by polymerizing the aromatic vinyl compound and the conjugated diene are polymerized. A method obtained by copolymerization (block copolymerization) with the obtained polymer (block (B)) is preferably exemplified.
Here, the number average molecular weight of the block (A) is preferably in the range of 3,000 to 50,000. When the molecular weight is within this range, the mechanical strength of the resulting styrenic thermoplastic elastomer is good, and the compression set resistance when obtaining the thermoplastic elastomer composition is good.
The number average molecular weight of the block (B) is preferably in the range of 10,000 to 200,000. When the molecular weight is within this range, the viscosity at the time of mixing and melting when obtaining a styrene-based thermoplastic elastomer composition becomes good.
Furthermore, the styrenic thermoplastic elastomer obtained as a block copolymer has one or more blocks (A) and one or more blocks (B), and the block form is A- (BA ) _N or (AB) _m . Among these, the form of A-B-A is preferable because fluidity and mechanical properties are improved, and a form of using AB and A-B-A together is also possible.

  In the present invention, the styrene thermoplastic elastomer preferably has a styrene content of 10 to 60% by mass, more preferably 30 to 50% by mass. When the styrene content is within this range, the viscosity at the time of mixing and melting when obtaining the thermoplastic elastomer composition becomes good, and the mechanical strength and compression set resistance of the thermoplastic elastomer composition are further improved.

Specific examples of such styrenic thermoplastic elastomers include, for example, hydrogenated styrene-isoprene block copolymer (SEPS: styrene ethylene propylene styrene block copolymer), styrene ethylene ethylene propylene styrene block copolymer. (Hereinafter referred to as “SEEPS”), styrene ethylene butylene styrene block copolymer (hereinafter referred to as “SEBS”), and the like.
In the present invention, commercially available products such as Septon 2006 (SEPS, manufactured by Kuraray Co., Ltd.), Septon 4055, and Septon 4077 (SEEPS, manufactured by Kuraray Co., Ltd.) can be used as such a styrenic thermoplastic elastomer.

  In the thermoplastic elastomer composition, the content of the styrenic thermoplastic elastomer is preferably 1 to 500 parts by mass, and preferably 30 to 200 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. More preferably, it is 50 to 150 parts by mass. When the content of the styrenic thermoplastic elastomer is within this range, the mechanical strength and compression set resistance of the resulting thermoplastic elastomer composition are further improved.

As a plasticizer, the well-known plasticizer used for a general resin composition and a rubber composition can be used. Specific examples include oils such as paraffin oil, process oil and aroma oil; liquid rubbers such as liquid polyisoprene (LIR), liquid polybutadiene (LBR) and liquid ethylene-propylene rubber (LEPM); tetrahydrophthalic acid, azelaic acid, Benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and derivatives thereof; dioctyl phthalate (DOP), dibutyl phthalate (DBP); polybutene; Dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate poly Ester, adipic acid butylene glycol polyester. These may be used alone or in combination of two or more.
Of these, oil and polybutene are preferably used from the viewpoint of oil bleeding and workability.

  In the thermoplastic elastomer composition, the content of the plasticizer is preferably 1 to 500 parts by weight, more preferably 5 to 300 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer. More preferably, it is 10-200 mass parts. When the content of the plasticizer is within this range, the flexibility and processability of the thermoplastic elastomer composition are further improved.

  In the present invention, it is one of preferred embodiments that the thermoplastic elastomer composition further contains an ethylene propylene copolymer having a polypropylene block and an ethylene propylene block. This aspect is excellent in flexibility and excellent in fluidity and mechanical strength at high temperature.

The ethylene-propylene copolymer has a polypropylene block and an ethylene-propylene block, and more specifically, a block composed of a polypropylene component (polypropylene block) and a block composed of a propylene / ethylene random copolymer component (ethylene-propylene block). Are block copolymers.
By containing such an ethylene propylene copolymer, the obtained thermoplastic elastomer composition retains excellent flexibility, and is excellent in fluidity and mechanical strength at high temperatures. This is because of the presence of polypropylene blocks with high crystallinity and hardness, mechanical strength such as heat resistance, modulus, and breaking strength is improved, and flexibility and fluidity at high temperatures are achieved due to the presence of ethylene-propylene blocks that are random copolymers. Is considered to be good.

  In the present invention, the ethylene propylene copolymer preferably has the polypropylene block in a proportion of 1 to 50 mol%, and has the polypropylene block in a proportion of 10 to 25 mol%. Is more preferable. When the proportion of the polypropylene block is within this range, the mechanical strength of the thermoplastic elastomer composition becomes better.

  In the present invention, the polypropylene block is preferably stereoregular from the viewpoint of better mechanical strength of the thermoplastic elastomer composition containing the ethylene-propylene copolymer, and the mechanical strength is further increased. It is preferably isotactic from the viewpoint of improvement.

  Furthermore, in the present invention, in the ethylene propylene block, other than propylene and ethylene, other polybutene components and the like may be contained in an amount of about 5% by mass or less as necessary.

  In this invention, it is preferable that it is 1-200 mass parts with respect to 100 mass parts of said thermoplastic elastomers, and, as for content of the said ethylene propylene copolymer, it is more preferable that it is 30-150 mass parts. When the content of the ethylene propylene copolymer is within this range, the fluidity and mechanical strength at a high temperature become better while maintaining the flexibility of the thermoplastic elastomer composition.

Conventionally, the soft material which consists of polyolefin resin is manufactured by mixing the amorphous ethylene propylene rubber (EPR) etc. which were manufactured using the vanadium catalyst in polypropylene.
In contrast, the ethylene-propylene copolymer used in the present invention is obtained by simultaneously polymerizing an elastomer component of polypropylene and a propylene / ethylene random copolymer using a titanium compound or an organoaluminum compound in one polymerization tank. Preferably it is manufactured. Alternatively, it may be produced by transferring separately synthesized polypropylene to another synthesis tank, charging ethylene and propylene therein, and polymerizing in the presence of a catalyst or the like.

  Such an ethylene propylene copolymer is preferably a so-called reactor type copolymer in which the ethylene content in the ethylene propylene block is increased. For example, it is commercially available as a soft type of prime TPO manufactured by Idemitsu Kosan Co., Ltd. What is marketed, specifically what is marketed by the brand name of M142E, is used suitably.

The thermoplastic elastomer composition preferably contains carbon black and / or silica as a reinforcing agent. The type of carbon black is appropriately selected according to the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle diameter. Soft carbon has low reinforcement to rubber, and hard carbon has strong reinforcement to rubber. In the present invention, it is particularly preferable to use hard carbon having strong reinforcing properties.
The content of carbon black (when used alone) is 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, and 1 to 80 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer. More preferably, it is part.

Silica is not particularly limited, and specifically, for example, fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, diatomaceous earth, etc., the content (when silica alone is used) is It is 0.1-200 mass parts with respect to 100 mass parts of thermoplastic elastomers, it is preferable that it is 1-100 mass parts, and it is more preferable that it is 1-80 mass parts. Of these, precipitated silica is preferred.
When silica is used as the reinforcing agent, a silane coupling agent can be used in combination. Examples of the silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide (Si69), bis (triethoxysilylpropyl) disulfide (Si75), γ-mercaptopropyltrimethoxysilane, and vinyltrimethoxysilane. Moreover, the aminosilane compound mentioned later can also be used.

  When carbon black and silica are used in combination, the content (total amount of carbon black and silica) is 0.1 to 200 parts by mass and 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. Is preferable, and it is more preferable that it is 1-80 mass parts.

  The thermoplastic elastomer composition may be a reinforcing agent other than a thermoplastic elastomer, a polymer other than a styrene-based thermoplastic elastomer and an ethylene-propylene copolymer, or a carbon black and a silica, if necessary, within a range not impairing the object of the present invention. (Filler), a filler obtained by introducing an amino group (hereinafter simply referred to as “amino group-introducing filler”), an amino group-containing compound other than the amino group-introducing filler, a compound containing a metal element (hereinafter “metal”) Salt "), maleic anhydride modified polymer, anti-aging agent, antioxidant, pigment, dye, thixotropic agent, UV absorber, flame retardant, solvent, surfactant (including leveling agent), dispersant In addition, various additives such as a dehydrating agent, a rust preventive agent, an adhesion imparting agent, an antistatic agent, and a filler can be contained.

As the additive and the like, commonly used ones can be used, and specific examples thereof are shown below, but are not limited to those exemplified.
As the polymer other than the thermoplastic elastomer, the styrene-based thermoplastic elastomer, and the ethylene propylene copolymer, a polymer having a glass transition temperature of 25 ° C. or lower is preferable as described above. Specifically, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), butyl rubber ( IIR), ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), ethylene-acrylic rubber (AEM), ethylene-butene rubber (EBM), etc., and particularly the unsaturated bond of IIR, EPM, EBM. Polymers that do not have them or polymers with low unsaturated bonds (eg EPDM) are preferred. A polymer having a site capable of hydrogen bonding is also preferable, and examples thereof include polyester, polylactone, and polyamide.
Further, in the thermoplastic elastomer composition, polymers other than the thermoplastic elastomer may be used alone or in combination of two or more, and the content of the polymer is based on 100 parts by mass of the thermoplastic elastomer. The amount is preferably 0.1 to 100 parts by mass, and more preferably 1 to 50 parts by mass.

  Specific examples of reinforcing agents other than carbon black and silica include, for example, iron oxide, zinc oxide, aluminum oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, and kaolin. Examples thereof include clay and fired clay. The content of these reinforcing agents is preferably 0.1 to 100 parts by mass, and more preferably 1 to 80 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.

  Examples of the filler that serves as a base for the amino group-introduced filler (hereinafter also simply referred to as “filler that serves as a base”) include the reinforcing agents exemplified as being optionally added to the composition. From the viewpoint of easy introduction of amino groups and easy adjustment of the introduction ratio (introduction ratio), silica, carbon black, and calcium carbonate are preferable, and silica is more preferable.

The amino group introduced into the filler serving as the substrate (hereinafter sometimes simply referred to as “amino group”) is not particularly limited, and specific examples thereof include aliphatic amino groups, aromatic amino groups, and complex groups. Examples thereof include an amino group constituting a ring and a plurality of mixed amino groups of these amino groups.
Here, in the present invention, the amino group of the aliphatic amine compound is an aliphatic amino group, the amino group bonded to the aromatic group of the aromatic amine compound is an aromatic amino group, and the amino group of the heterocyclic amine compound is an amino group. It is called a heterocyclic amino group.
Among these, from the viewpoint of moderately forming an interaction with the thermoplastic elastomer and being effectively dispersible in the thermoplastic elastomer, a heterocyclic amino group, a mixed amino group containing a heterocyclic amino group, or an aliphatic group An amino group is preferable, and a heterocyclic amino group or an aliphatic amino group is preferable.

The series of the amino group is not particularly limited, and is primary (—NH ₂ ), secondary (imino group,> NH), tertiary (> N—) or quaternary (> N ⁺ <). Any of these may be used.
When the amino group is primary, the interaction with the thermoplastic elastomer tends to be strong, and gelation may occur depending on the conditions for preparing the composition. On the other hand, when the amino group is tertiary, the interaction with the thermoplastic elastomer tends to be weak, and the improvement effect such as compression set resistance when used as a composition may be small.
From such a viewpoint, the series of the amino group is preferably primary or secondary, and more preferably secondary.

  That is, the amino group is preferably a heterocyclic amino group, a mixed amino group containing a heterocyclic amino group, or a primary or secondary aliphatic amino group, and is preferably a heterocyclic amino group or a primary or secondary amino group. More preferably, it is a secondary aliphatic amino group.

  It is sufficient that at least one amino group is present on the surface of the filler serving as the substrate. However, it is preferable to have a plurality of amino groups from the viewpoint of an excellent improvement effect such as resistance to compression set when used as a composition.

In the case of having a plurality of amino groups, at least one of the plurality of amino groups is preferably a heterocyclic amino group, and further a primary or secondary amino group (aliphatic amino group, aromatic amino group). It is more preferable to have a heterocyclic amino group.
Moreover, the kind and series of an amino group can arbitrarily adjust the said amino group according to the physical property requested | required of a composition.

The amino group-introduced filler is obtained by introducing the amino group into the filler serving as the substrate.
The method for introducing the amino group is not particularly limited, and specific examples thereof include surface treatment methods (for example, surface modification methods, surface coating methods) generally used for various fillers, reinforcing agents, and the like. It is done. Preferable methods include, for example, a method in which a compound having a functional group and an amino group capable of reacting with the filler serving as the substrate is reacted with the filler (surface modification method), and filling the substrate with the polymer having an amino group. Examples thereof include a method of coating the surface of the agent (surface coating method), and a method of reacting a compound having an amino group in the synthesis process of the filler.

The amino group-introduced fillers may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to an arbitrary ratio according to the use of the suction pad, the required physical properties, and the like.
The content of the amino group-introduced filler is preferably 0.1 to 200 parts by mass, more preferably 10 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the thermoplastic elastomer. More preferably.

The amino group-containing compound other than the amino group-introduced filler will be described.
The amino group in the amino group-containing compound is basically the same as that described in the amino group-introduced filler, and is not particularly limited as long as the amino group content is 1 or more. The above is preferable because it can form two or more cross-linked bonds with the thermoplastic elastomer and is excellent in the effect of improving physical properties.

The series of the amino group in the amino group-containing compound is not particularly limited, and is similar to the amino group in the amino group-introduced filler, primary (—NH ₂ ), secondary (imino group,> NH), It may be either tertiary (> N−) or quaternary (> N ⁺ <), and is required for the thermoplastic elastomer composition to be recycled, compression set, hardness and mechanical strength, particularly tensile It can be arbitrarily selected according to physical properties such as strength. When a secondary amino group is selected, the mechanical strength tends to be excellent, and when a tertiary amino group is selected, the recyclability tends to be excellent. In particular, it is preferable to have two secondary amino groups because the thermoplastic elastomer composition obtained is excellent in recyclability, compression set resistance and mechanical strength, and in the balance of these physical properties.
When the amino group-containing compound contains two or more amino groups, the number of primary amino groups in the amino group-containing compound is preferably 2 or less, and 1 or less. More preferably. When there are 3 or more primary amino groups, the (crosslinking) bond formed by the amino groups and the functional groups in the thermoplastic elastomer (particularly carboxy groups, which are carbonyl-containing groups) is strengthened and has excellent recyclability. May be damaged.

  In other words, the amino group series and number, and the structure of the amino group-containing compound can be appropriately adjusted and selected in consideration of the bonding strength between the functional group in the thermoplastic elastomer and the amino group in the amino group-containing compound. .

Specific examples of such an amino group-containing compound include N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dimethyl-1,3- Propanediamine, N, N'-diethyl-1,3-propanediamine, N, N'-diisopropyl-1,3-propanediamine, N, N'-dimethyl-1,6-hexanediamine, N, N'- Secondary aliphatic diamines such as diethyl-1,6-hexanediamine and N, N ′, N ″ -trimethylbis (hexamethylene) triamine; Tertiary fats such as tetramethyl-1,6-hexanediamine Diamines; polyamines containing aromatic primary amines such as aminotriazole and aminopyridine and heterocyclic amines; linear chains such as dodecylamine Rukirumonoamin; tertiary heterocyclic diamines such as dipyridyl, compression set, mechanical strength, improvement effect of particularly tensile strength and the like are suitably exemplified a high reasons.
Of these, secondary aliphatic diamines, polyamines containing aromatic primary amines and heterocyclic amines, or tertiary heterocyclic diamines are more preferred.

  In addition to these examples, a polymer compound having an amino group can be used as the amino group-containing compound.

The polymer compound having an amino group is not particularly limited, and specific examples thereof include polyamide, polyurethane, urea resin, melamine resin, polyvinylamine, polyallylamine, polyacrylamide, polymethacrylamide, polyaminostyrene, amino group-containing poly Examples thereof include polymers such as siloxane, and polymers obtained by modifying various polymers with a compound having an amino group.
The physical properties such as the average molecular weight, molecular weight distribution, and viscosity of these polymers are not particularly limited, and can be set to any physical properties depending on the use of the adsorption pad, the required physical properties, and the like.

  The polymer compound having an amino group is preferably a polymer obtained by polymerizing (polyaddition or polycondensation) a condensable or polymerizable compound (monomer) having an amino group. A polysiloxane having an amino group that is a single condensate of a silyl compound having a group or a cocondensate of a silyl compound and a silyl compound not having an amino group is easy to obtain, easy to manufacture, and has a molecular weight It is more preferable because adjustment, adjustment of amino group introduction rate, and the like are easy.

The silyl compound having a hydrolyzable substituent and an amino group is not particularly limited, and examples thereof include aminosilane compounds. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ -An aliphatic primary amino group such as aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane (available from Nihon Unicar) Aminosilane compounds; N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3-triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxysilyl) Propyl] amine (available from Nihon Unicar), 3- (n-butylamino) propyltrime Aminosilane compounds having an aliphatic secondary amino group such as xylsilane (for example, Dynasilane 1189 (manufactured by Degussa Huls)), N-ethyl-aminoisobutyltrimethoxysilane (for example, Silquest A-Link 15 silane, manufactured by OSi Specialties) N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane (from Nihon Unicar) An aminosilane compound having an aliphatic primary and secondary amino group such as N-phenyl-γ-aminopropyltrimethoxysilane (available from Nihon Unicar) and the like. Aminosilane compound having; Dazole trimethoxysilane (available from Japan Energy Co., Ltd.), a complex such as triazolesilane obtained by reacting aminotriazole with an epoxy silane compound or isocyanate silane compound in the presence or absence of a catalyst at a temperature above room temperature An aminosilane compound having a cyclic amino group is exemplified.
Among these, from the viewpoint of a high effect of improving physical properties such as compression set resistance, the above-mentioned aminosilane compounds having an aliphatic primary amino group, aminosilane compounds having an aliphatic secondary amino group, and aliphatic primary Aminosilane compounds having primary and secondary amino groups are preferred.

The silyl compound not having an amino group is not particularly limited as long as it is a compound different from the silyl compound having a hydrolyzable substituent and an amino group and does not contain an amino group. Examples include alkoxysilane compounds and halogenated silane compounds. Of these, alkoxysilane compounds are preferred from the viewpoints of availability, ease of handling, and excellent physical properties of the resulting cocondensate.
Specific examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, and methyltriisopropoxysilane. , Phenyltrimethoxysilane, and dimethyldimethoxysilane.
Specific examples of the halogenated silane compound include tetrachlorosilane and vinyltrifluorosilane.
Of these, tetraethoxysilane and tetramethoxysilane are preferred from the viewpoint of low cost and safe handling.

  The silyl compound having a hydrolyzable substituent and an amino group and the silyl compound not having an amino group may be used alone or in combination of two or more.

  Such polymer compounds having an amino group may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to an arbitrary ratio according to the use of the suction pad, the required physical properties, and the like.

The content of the polymer compound having an amino group can be defined by the number of nitrogen atoms (equivalent) in the polymer compound with respect to the side chain of the thermoplastic elastomer as in the case of the amino group-containing compound. There may be an amino group that cannot effectively form an interaction with the thermoplastic elastomer depending on the structure and molecular weight of the compound.
Therefore, the content of the polymer compound having an amino group is preferably 1 to 200 parts by mass, more preferably 5 parts by mass or more, with respect to 100 parts by mass of the thermoplastic elastomer. More preferably.

The metal salt is not particularly limited as long as it is a compound containing at least one metal element, and is composed of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Al. A compound containing one or more metal elements selected from the group is preferable.
Specific examples of the metal salt include saturated fatty acid salts having 1 to 20 carbon atoms such as formate, acetate and stearate containing one or more of these metal elements, and (meth) acrylates. And a complex with an unsaturated fatty acid salt such as a metal alkoxide (reactant with an alcohol having 1 to 12 carbon atoms), nitrate, carbonate, bicarbonate, chloride, oxide, hydroxide, or diketone.
Here, the “complex with diketone” refers to a complex in which 1,3-diketone (for example, acetylacetone) or the like is coordinated to a metal atom.

  Of these, from the viewpoint of further improving the compression set of the resulting thermoplastic elastomer composition, Ti, Al, and Zn are preferred as the metal element, and the metal salts such as acetate, stearate, and the like are preferred. C1-C20 saturated fatty acid salts, metal alkoxides (reactants with C1-C12 alcohols), oxides, hydroxides, complexes with diketones are preferred, and C1-C20 such as stearates. Saturated fatty acid salts, metal alkoxides (reactants with alcohols having 1 to 12 carbon atoms), and complexes with diketones are more preferred.

  The said metal salt may be used individually by 1 type, or may be used together 2 or more types. The mixing ratio in the case of using two or more kinds in combination can be set to any ratio depending on the use of the suction pad, the required physical properties, and the like.

  The content of the metal salt is preferably 0.05 to 3.0 equivalents, more preferably 0.1 to 2.0 equivalents, based on the carbonyl group contained in the thermoplastic elastomer. More preferably, it is 2 to 1.0 equivalent. When the content of the metal salt is within this range, the thermoplastic elastomer composition obtained is preferably improved in physical properties such as resistance to compression set, hardness and mechanical strength, particularly tensile strength.

The metal salt may be any hydroxide, metal alkoxide, carboxylate, or the like that the metal can take. For example, taking a hydroxide as an example, when the metal is iron, Fe (OH) ₂ and Fe (OH) ₃ may be used alone or in combination.
Further, as described above, the metal salt is one or more selected from the group consisting of Li, Na, K, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Al. Although it is preferable that it is a compound containing a metal element, you may contain metal elements other than these in the range which does not impair the objective of this invention. Although the content rate of metal elements other than these is not specifically limited, For example, it is preferable that it is 1-50 mol% with respect to all the metal elements in the said metal salt.

  The maleic anhydride modified polymer is a polymer obtained by modifying the elastomeric polymer with maleic anhydride, and the side chain of the maleic anhydride modified polymer is other than the maleic anhydride residue and the nitrogen-containing heterocyclic ring. Although it may have a functional group, it preferably has only a maleic anhydride residue.

The maleic anhydride residue is introduced (modified) into the side chain or terminal of the elastomeric polymer and is not introduced into the main chain of the elastomeric polymer. The maleic anhydride residue is a cyclic acid anhydride group, and the cyclic acid anhydride group (part) does not open.
Therefore, as the maleic anhydride-modified thermoplastic polymer, for example, as shown in the following formula (26), an ethylenically unsaturated bond portion of maleic anhydride is obtained by reacting with an elastomeric polymer, and a cyclic acid is added to the side chain. Examples include thermoplastic elastomers having an anhydride group and no nitrogen-containing heterocycle, and specific examples thereof include those exemplified for the above-described elastomeric polymer containing a cyclic acid anhydride group in the side chain. .

（式中、Ｑはエチレン残基またはプロピレン残基であり、ｐ、ｑおよびｒはそれぞれ独立に０．１〜９９の数を表す。）

(In the formula, Q is an ethylene residue or a propylene residue, and p, q and r each independently represents a number of 0.1 to 99.)

  The amount of maleic anhydride modification is preferably 0.1 to 50 mol% with respect to 100 mol% of the main chain portion of the elastomeric polymer from the viewpoint of improving compression set resistance without impairing excellent recyclability. More preferably, it is 0.3-30 mol%, More preferably, it is 0.5-10 mol%.

  The maleic anhydride-modified polymer may be used alone or in combination of two or more. The mixing ratio when two or more kinds are used in combination can be set to an arbitrary ratio according to the use of the suction pad, the required physical properties, and the like.

The content of the maleic anhydride-modified polymer is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. When the content of the maleic anhydride-modified polymer is within this range, the processability and mechanical strength of the resulting thermoplastic elastomer composition are improved, which is preferable.
In the production of the thermoplastic elastomer, specifically, in the reaction step A or B, when an elastomeric polymer containing a cyclic acid anhydride group in the side chain as an unreacted substance remains, Without removing the group-modified elastomer, it can also be contained in the thermoplastic elastomer composition as it is.

Specific examples of the anti-aging agent include hindered phenol compounds, aliphatic and aromatic hindered amine compounds, and the like.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the pigment include, for example, titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, and other inorganic pigments, azo pigments, copper phthalocyanine pigments, and the like. And organic pigments.

Specific examples of the thixotropic agent include benton, silicic anhydride, silicic acid derivatives, and urea derivatives.
Specific examples of the ultraviolet absorber include 2-hydroxybenzophenone, benzotriazole, and salicylic acid ester.
Specific examples of the flame retardant include phosphorus such as TCP, halogen such as chlorinated paraffin and perchlorpentacyclodecane, antimony such as antimony oxide, and aluminum hydroxide.

Specific examples of the solvent include hydrocarbons such as hexane and toluene; halogenated hydrocarbons such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; And ester systems such as
Specific examples of the surfactant (leveling agent) include polybutyl acrylate, polydimethylsiloxane, a modified silicone compound, and a fluorine-based surfactant.
Specific examples of the dehydrating agent include vinyl silane.

Specific examples of the rust inhibitor include zinc phosphate, tannic acid derivatives, phosphate esters, basic sulfonates, and various rust preventive pigments.
Specific examples of the adhesion-imparting agent include known silane coupling agents, silane compounds having an alkoxysilyl group, titanium coupling agents, and zirconium coupling agents. More specifically, examples include trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  The content of the plasticizer is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. The content of other additives is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.

Some thermoplastic elastomers can be self-crosslinked, but a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, a vulcanization retarder, and the like can be used in combination as long as the object of the present invention is not impaired.
Examples of the vulcanizing agent include sulfur-based, organic peroxide-based, metal oxide-based, phenolic resin, quinone dioxime, and the like.
Specific examples of the sulfur-based vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide.
Specific examples of the organic peroxide vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di- (T-Butylperoxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate).
In addition, magnesium oxide, risurge (lead oxide), p-quinonedioxime, tetrachloro-p-benzoquinone, p-dibenzoylquinonedioxime, poly-p-dinitrosobenzene, methylenedianiline, and the like can be given.

Specific examples of the vulcanization aid include zinc oxide, magnesium oxide, amines; fatty acids such as acetic acid, propionic acid, butanoic acid, stearic acid, acrylic acid, maleic acid; zinc acetylate, zinc propionate And fatty acid zinc such as zinc butanoate, zinc stearate, zinc acrylate and zinc maleate.
Specific examples of the vulcanization accelerator include thiurams such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD); aldehydes and ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine; Thiazoles such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide (DM); sulfenes such as N-cyclohexyl-2-benzothiazylsulfenamide and Nt-butyl-2-benzothiazylsulfenamide Amide type is mentioned. Furthermore, alkylphenol resins and their halides can also be used.
Specific examples of the vulcanization retarder include organic acids such as phthalic anhydride, benzoic acid, salicylic acid and acetylsalicylic acid; N-nitroso-diphenylamine, N-nitroso-phenyl-β-naphthylamine, N-nitroso- Nitroso compounds such as polymers of trimethyl-dihydroquinoline; halides such as trichloromelanin; 2-mercaptobenzimidazole; N- (cyclohexylthio) phthalimide (for example, Suntogard PVI manufactured by FLEXSYS).
The content of these vulcanizing agents is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.

  The method for producing the thermoplastic elastomer composition is not particularly limited. For example, the thermoplastic elastomer and various additives that may be contained as necessary are mixed by a roll, a kneader, an extruder, a universal agitator, or the like. That's fine.

  Curing conditions when the thermoplastic elastomer composition is permanently crosslinked (with a vulcanizing agent) can be appropriately selected according to various components to be blended, and are not particularly limited. For example, curing conditions for curing at a temperature of 130 to 200 ° C. for 5 to 60 minutes are preferable.

When the thermoplastic elastomer composition is heated to about 80 to about 200 ° C., the three-dimensional crosslinked bond (crosslinked structure) is dissociated and softened to impart fluidity. This is considered to be because the interaction between the side chains formed between the molecules or within the molecule is weakened.
When the thermoplastic elastomer composition softened and fluidized is allowed to stand at about 80 ° C. or less, the dissociated three-dimensional crosslinked bond (crosslinked structure) is bonded again and cured. By repeating this, recyclability of the thermoplastic elastomer composition is manifested, and the adsorption part can be recycled.

In the present invention, the material of the base portion is not particularly limited. For example, the material used for a conventionally known suction pad can be used, but the same thermoplastic elastomer composition used for the above-described suction portion is used. Is preferably used.
Among these, it is preferable to integrally mold the base portion and the suction portion by injection molding or the like.

  The suction pad of the present invention is recyclable, has excellent adsorptivity, and does not cause deformation of the object to be adsorbed, and therefore is suitably used for a wide range of applications.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Preparation of thermoplastic elastomer composition (1) Thermoplastic elastomer composition 1
In a pressure kneader heated to 200 ° C., maleic anhydride-modified EPM (prototype manufactured by Mitsui Chemicals), olefin-based soft resin (Thermoplastic olefinic elastomer (TPO), Prime TPO M142E, manufactured by Idemitsu Kosan Co., Ltd.), maleic anhydride modified PP (Admer QF500, manufactured by Mitsui Chemicals), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS, Septon 4077, manufactured by Kuraray Co., Ltd.) and phenolic anti-aging agent (IRGANOX 1010, manufactured by Nagase Sangyo Co., Ltd.) After charging at the rate shown in Table 1 and masticating for 5 minutes, polybutene (HV-100, manufactured by Nippon Petrochemical Co., Ltd.) was added at the rate shown in Table 1. After mixing for 10 minutes, trifunctional alcohol (Uniox G450, manufactured by NOF Corporation) was added at a ratio shown in Table 1. Further, after kneading for 5 minutes, titanium oxide (Typaque R-820, manufactured by Teika), color master (PIGMENT GREEN 401E, manufactured by Sanyo Dye) and internal mold release agent (Strectol HT204, manufactured by S & S Japan Co., Ltd.) It added in the ratio shown in Table 1. After kneading for 5 minutes, it was discharged to obtain a pellet-shaped thermoplastic elastomer composition 1.

(2) Thermoplastic elastomer composition 2
In a pressure kneader heated to 200 ° C., maleic anhydride-modified EPM (prototype manufactured by Mitsui Chemicals), olefin-based soft resin (Thermoplastic olefinic elastomer (TPO), Prime TPO M142E, manufactured by Idemitsu Kosan Co., Ltd.), maleic anhydride modified PP (Admer QF500, manufactured by Mitsui Chemicals), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene (SEEPS, Septon 4077, manufactured by Kuraray Co., Ltd.) and phenolic anti-aging agent (IRGANOX 1010, manufactured by Nagase Sangyo Co., Ltd.) After charging at the rate shown in Table 1 and masticating for 5 minutes, polybutene (HV-100, manufactured by Nippon Petrochemical Co., Ltd.) was added at the rate shown in Table 1. After mixing for 10 minutes, trifunctional alcohol (Uniox G450, manufactured by NOF Corporation) was added at a ratio shown in Table 1. After kneading for 15 minutes, 3-amino-1,2,4-triazole (TMG, manufactured by Nippon Carbide Industries Co., Ltd.) was added in the ratio shown in Table 1. Further, after kneading for 5 minutes, titanium oxide (Typaque R-820, manufactured by Teika), color master (PIGMENT GREEN 401E, manufactured by Sanyo Dye) and internal mold release agent (Strectol HT204, manufactured by S & S Japan Co., Ltd.) It added in the ratio shown in Table 1. After kneading for 5 minutes, it was discharged to obtain a pellet-shaped thermoplastic elastomer composition 2.

2. Evaluation of Thermoplastic Elastomer Composition The thermoplastic elastomer composition 1 and the thermoplastic elastomer composition 2 obtained above and the olefinic thermoplastic elastomer (Thermorun 3705N, manufactured by Mitsubishi Chemical Corporation, dynamic cross-linking type) are as follows. JIS A hardness and 100% modulus (M ₁₀₀ ) were measured. The results are shown in Table 2.
In addition, a recycle test was performed as follows, and the rate of change in tensile stress (T _B ) at break and elongation (E _B ) at break was measured. The results are shown in Table 2.

(1) JIS A hardness After thermo-press molding the thermoplastic elastomer composition 1 and the like at 200 ° C. for 10 minutes, a flat plate sample having a thickness of 2 cm × length 15 cm × width 15 cm is prepared, according to the provisions of JIS K6253-1997. , JIS A hardness was measured.

(2) 100% modulus (M ₁₀₀ )
After the thermoplastic elastomer composition 1 or the like is hot press molded at 200 ° C. for 10 minutes, a dumbbell-shaped test piece (dumbbell-shaped No. 3) having a thickness of 2 mm is obtained from the vulcanized rubber composition according to JIS K6251-1993. Was punched out, and a tensile test was performed under the condition of a tensile speed of 500 mm / min, and a 100% modulus (M ₁₀₀ ) was measured.

(3) Recycling test The thermoplastic elastomer composition 1 and the like were hot press molded at 200 ° C. for 10 minutes to produce a 15 cm × 15 cm × 2 mm sheet. A JIS No. 3 dumbbell-shaped test piece was punched from this sheet. The test piece was pulled at a speed of 500 mm / min, and the tensile stress at break (T _B ) and the elongation at break (E _B ) were measured.
Separately, the thermoplastic elastomer composition 1 and the like were hot press molded at 200 ° C. for 10 minutes to produce a 15 cm × 15 cm × 2 mm sheet, and the obtained sheet was chopped with scissors. After shredding, a recycling process was performed in which pellets were formed and sheets were produced by the same method as described above. This recycling process was further repeated for a total of 3 times. Thereafter, T _B and E _B were measured by the same method as described above.
For each T _B and E _B, the value value obtained by subtracting the post-recycled 3 times from the initial value was divided by the initial value, was calculated T _B change rate and the E _B rate of change.

3. Preparation of suction pads (Examples 1 and 2 and Comparative Example 1)
As shown in Table 2, any one of the thermoplastic elastomer composition 1 and the thermoplastic elastomer composition 2 obtained above and an olefin-based thermoplastic elastomer (Thermolan 3705N, manufactured by Mitsubishi Chemical Corporation, dynamic cross-linking type) is used. It was used for injection molding to obtain a suction pad having the shape and dimensions shown in FIG.

4). Evaluation of adsorption pad After connecting a vacuum generator to the adsorption pad obtained above, adsorption and desorption of a plastic plate made of polypropylene of 297 mm x 210 mm x 2 mm were repeated 300,000 times. The presence or absence of deformation was evaluated. The degree of vacuum inside the suction pad at the time of suction was set to -93.3 kPa.
The results are shown in Table 2. In the table, regarding the adsorptivity, those that could stably perform the adsorption of the plastic plate were determined as “good”, and those that could not be stably performed were determined as “bad”. In addition, regarding the deformation of the adsorbed material, “none” was given when the plastic plate was not deformed, and “present” when it was seen.

From Table 2, it can be seen that the suction pads of the present invention (Examples 1 and 2) are excellent in adsorptivity and have no deformation of the object to be adsorbed. This is presumably because the hardness is low and the flexibility is high, so that the followability to the shape of the object to be adsorbed is excellent. Moreover, the adsorption pad of the present invention has a low rate of change in physical properties after recycling.
On the other hand, when the thermoplastic elastomer conventionally used for the suction pad was used (Comparative Example 1), the adsorptivity was inferior, and the object to be adsorbed was deformed.

It is a schematic diagram which shows an example of the suction pad of this invention.

Explanation of symbols

10 Adsorption pad 12 Base 14 Adsorption part

Claims (8)

A suction pad comprising a cylindrical base and a skirt-like suction part connected to one end of the base,
The adsorbing part is composed of a thermoplastic elastomer composition containing a thermoplastic elastomer,
The adsorption pad in which the thermoplastic elastomer contains a hydrogen-bonding cross-linking site having a carbonyl-containing group, a covalent cross-linking site and / or a nitrogen-containing heterocycle in the side chain.   The suction pad according to claim 1, wherein the thermoplastic elastomer composition further contains a styrene thermoplastic elastomer having a weight average molecular weight of 100,000 or more and a plasticizer.   The adsorption pad according to claim 1 or 2, wherein the thermoplastic elastomer composition further contains an ethylene propylene copolymer having a polypropylene block and an ethylene propylene block.   The thermoplastic elastomer can be cross-linked by at least one bond selected from the group consisting of amide, ester, lactone, urethane, ether, thiourethane and thioether at the covalent cross-linking site. The suction pad according to any one of the above. The adsorption pad in any one of Claims 1-4 in which the side chain containing the said hydrogen bond bridge | crosslinking site | part contains the structure represented by following formula (1).

(In the formula, A is a nitrogen-containing heterocyclic ring, B is a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) or a sulfur atom, or these An organic group that may contain atoms or groups.) The side chain containing the hydrogen-bonding crosslinking site contains a structure represented by the following formula (2) or (3) bonded to the main chain at the α-position or β-position. The suction pad described in 1.

(Wherein A is a nitrogen-containing heterocyclic ring, B and D are each independently a single bond; an oxygen atom, an amino group NR ′ (R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)) or Sulfur atom or organic group optionally containing these atoms or groups.) The suction pad according to any one of claims 1 to 6, wherein the covalently crosslinked site contains a structure represented by the following formula (4A).

(In the formula, R is a single bond, an oxygen atom or a sulfur atom, or an organic group which may contain these atoms or groups.) The adsorption pad according to claim 7, wherein the covalently crosslinked site contains a structure represented by the following formula (7A) bonded to the main chain at the α-position or the β-position.

(In the formula, R is a single bond, an oxygen atom or a sulfur atom, or an organic group which may contain these atoms or groups.)

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