JP2011094067A - Semiconductive cross-linkable compound and cross-linked rubber of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pale-colored cross-linked rubber reduced in adhesion of dust and risk of discharge breakdown due to static electricity of a contacting electrical/electronic component. <P>SOLUTION: In the cross-linked rubber obtained by curing a cross-linkable compound, a surface resistance is 10<SP>9</SP>Ω/SQUARE or less, or a volume specific resistance is 10<SP>9</SP>Ωcm or less. The cross-linkable compound includes the following components as essential components: (A) at least one polymer selected from (a-1) a polyoxyalkylene polymer having one or more alkenyl groups on average in one molecule and having number-average molecular weight of 3,000-50,000 and (a-2) a poly(meth)acrylic polymer having one or more alkenyl groups on average in one molecule, a main chain produced by polymerizing (meth)acrylic monomers principally, and number-average molecular weight of 3,000-50,000; (B) a compound having at least two hydrosilyl groups on average in one molecule; (C) a hydrosilylation catalyst; and (D) a pale-colored conductive metal oxide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a crosslinkable compound that forms a semiconductive crosslinked rubber by heating, and a semiconductive crosslinked rubber obtained from the composition.

  In recent years, as semiconductor elements and electronic / electrical components have become more precise, adhesion of dust and discharge breakdown due to static electricity have become major problems. Antistatics for assembly lines of electrical equipment and transfer of parts containers, etc.・ Manufacturing processes such as static electricity removal in the transfer line are forced to bear a heavy burden on countermeasure management.

  On the other hand, rubber parts are widely used as parts for electronic and electrical products, manufacturing processes such as semiconductors and semiconductors, making use of functions such as sealing, vibration and shock absorption, adhesion and adhesion. Yes.

  Accordingly, there is an increasing number of cases in which such rubber parts are also required to take measures against the adhesion of dust and the discharge breakdown due to static electricity. As a general countermeasure, a method of imparting conductivity to the rubber itself is employed. As a specific method, a method of blending a conductive substance with rubber or applying a conductive coating on the rubber surface is adopted.

  However, in the latter case, it is necessary to provide a new process for coating the surface, and when the coating layer is thin, its durability becomes a problem, and post-processing such as cutting after surface coating is difficult. There are many issues and restrictions.

Moreover, as a method for imparting conductivity to the former rubber itself, carbon black is generally used in many cases, but a semiconductive region of about 10 ⁴ to 10 ⁹ Ω · cm, which is often used as an antistatic, is used. There are problems such as difficulty in control, carbon black being easily scattered and surroundings being easily contaminated, and coloring being difficult. In particular, rubber parts are often required to be colored from the viewpoint of appearance or product identification, and there is a strong demand for rubber having light-colored semiconductivity.

  Therefore, in such a case, a metal oxide is used as a light color conductivity imparting agent. Specific examples thereof include a conductive polyorganosiloxane composition in which a metal oxide light-colored conductive filler is added to moisture-curing silicone rubber (Patent Document 1), and a curable resin of a transparent conductive laminate. Example of containing ultrafine particles made of metal oxide or metal fluoride in synthetic rubber component as layer (Patent Document 2), and plastisol sealing material composition containing conductive metal oxide in rubber, cross-linked polyether resin or the like (Patent Document 3) is known.

  On the other hand, conventionally, a crosslinked rubber obtained by a hydrosilylation reaction of a polymer having an alkenyl group and a crosslinking agent having a hydrosilyl group has been known, and it can be cured at a relatively low temperature as a heat-curable rubber. In addition, it is recognized as a characteristic crosslinked rubber material that can be applied to a wide range of molding methods because it has a high curing speed, small shrinkage during curing, and can be designed to have fluidity before curing. As the polymer, an oxypropylene polymer having excellent low-temperature rubber elasticity (Patent Document 4), an acrylate polymer having excellent oil resistance (Patent Document 5), and the like are known. However, the hydrosilylation reaction, which is a crosslinking reaction, is susceptible to reaction inhibition by nitrogen atoms, sulfur atoms, phosphorus atoms, etc., and there are limited fillers and additives that can be used practically. Sex rubber has not been known so far.

JP-A-5-239357 JP 2007-42284 A JP 2009-185249 A Japanese Patent No. 3472340 Japanese Patent No. 2927892

  The present invention is based on a polyoxypropylene polymer and a polyacrylate polymer using a hydrosilylation reaction for a cross-linking reaction, which reduces the risk of discharge damage due to dust adhesion and static electricity of electric / electronic parts in contact. An object of the present invention is to provide a cross-linked rubber having the characteristics described above. Furthermore, these crosslinkable compounds are light-colored, and by adding a pigment or the like to the composition, the finally obtained crosslinked rubber can be colored.

In order to solve the above-mentioned technical problem, the semiconductive crosslinkable compound according to claim 1 of the present invention contains the following components (A) to (D) as essential components, and is a crosslinked rubber SRIS 2304 obtained by curing. The surface resistance value measured by the above method is 10 ⁹ Ω / □ or less, or the volume resistivity value is 10 ⁹ Ω · cm or less.
(A) (a-1) a polyoxyalkylene polymer having a number average molecular weight of 3,000 to 50,000 having an average of more than one alkenyl group in one molecule, (a-2) an average in one molecule At least selected from poly (meth) acrylic polymers having a number average molecular weight of 3,000 to 50,000 and having a alkenyl group exceeding 1 and the main chain produced mainly by polymerizing a (meth) acrylic monomer At least one polymer selected from the group consisting of one kind (B) Compound having at least two hydrosilyl groups in one molecule (C) Hydrosilylation catalyst (D) Light color conductive metal oxide The semiconductive crosslinkable compound according to claim 2 of the invention is characterized in that the light-colored conductive metal oxide as the component (D) is a metal oxide surface-treated with a conductive material.
Further, in the semiconductive crosslinkable compound according to claim 3 of the present invention, the light-colored conductive metal oxide as the component (D) is doped with titanium oxide or antimony surface-treated with antimony-doped tin oxide. And at least one selected from the group consisting of potassium titanate surface-treated with tin oxide or zinc oxide surface-treated with aluminum.
Further, in the semiconductive crosslinkable compound according to claim 4 of the present invention, the component (A) is (a-1), and the conductive filler (D) is a component (A) to (D). It is characterized by having a volume fraction of 5% or more in the semiconductive crosslinkable compound containing the component as an essential component.
Further, in the semiconductive crosslinkable compound according to claim 5 of the present invention, the (A) component is (a-2), and the conductive filler (D) is a component (A) to (D). The volume fraction of the semiconductive crosslinkable compound containing the component as an essential component is 10% or more.
The semiconductive crosslinkable compound according to claim 6 of the present invention is characterized in that a light-colored filler is an essential component as the component (E).
Moreover, the semiconductive crosslinkable compound according to claim 7 of the present invention is characterized in that the light-colored filler as the component (E) is finely divided silica.
Moreover, the semiconductive crosslinkable compound according to claim 8 of the present invention is characterized in that the hydrosilylation catalyst as the component (C) is a platinum complex compound, and the platinum concentration is 10 ppm or more as a whole.
In addition, in the semiconductive crosslinkable compound according to claim 9 of the present invention, the poly (meth) acrylic polymer as the component (a-2) is composed of ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate. And at least one selected from the group consisting of 2-methoxybutyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate as a monomer unit.
In the semiconductive crosslinkable compound according to claim 10 of the present invention, the main chain of the poly (meth) acrylic polymer as the component (a-2) is produced by a living radical polymerization method. It is characterized by.
The semiconductive crosslinkable compound according to claim 11 of the present invention is characterized in that the component (B) is an organohydrogenpolysiloxane having an average of at least two hydrosilyl groups in one molecule.
Moreover, Claim 12 of this invention is the semiconductive crosslinked rubber obtained from the semiconductive crosslinkable compound of any one of the said Claims 1-11.
A thirteenth aspect of the present invention is a semiconductive crosslinked rubber obtained from the semiconductive crosslinkable compound according to any one of the first to eleventh aspects and used for vibration / impact absorption. is there.
Moreover, Claim 14 of this invention is a semiconductive bridge | crosslinking used for the purpose of fixation and / or temporary fixation obtained from the semiconductive crosslinkable compound of any one of the said Claims 1-11. It is rubber.
The fifteenth aspect of the present invention is a semiconductive cross-linked rubber used for the purpose of sealing, obtained from the semiconductive cross-linkable compound according to any one of the first to eleventh aspects.

That is, the present invention provides a light-colored semiconductive rubber composition having an electric resistance of 10 ⁹ Ω or less, which is effective for preventing charging, and a crosslinked rubber thereof.

  Hereinafter, embodiments of the semiconductive rubber composition and the crosslinked rubber according to the present invention will be described in detail.

The number average molecular weight of 3,000 to 50,000 polyoxyalkylene polymer having more than one alkenyl group in one molecule, which is the component (a-1) of the present invention, is not particularly limited and is publicly known. Things. Specifically, the main chain skeleton of the polymer has a repeating unit represented by the general formula (1).
Formula (1): —R ¹ —O— (1)
(Wherein R ¹ is a divalent alkylene group)
R ¹ in the general formula (1) is not particularly limited as long as it is a divalent alkylene group. Among them, an alkylene group having 1 to 14 carbon atoms is preferable, and a linear or branched chain having 2 to 4 carbon atoms. The alkylene group is more preferable. The repeating unit described in the general formula (1) is not particularly limited. For example, —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H ₅ ) O—, —CH ₂ C (CH ₃ ) ₂ O—, —CH ₂ CH ₂ CH ₂ CH ₂ O— and the like.

The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit or may be a combination of a plurality of repeating units. Among these, a polymer composed of —CH ₂ CH (CH ₃ ) O— as the main repeating unit is preferable because it is easily available and has excellent workability. In addition, a repeating unit other than the oxyalkylene unit may be contained in the main chain skeleton of the polymer. In this case, the total proportion of oxyalkylene units contained in the polymer is preferably 80% by weight or more, particularly 90% by weight or more.

  The main chain skeleton of the polymer of component (a-1) may be a linear polymer, a branched polymer, or a mixture thereof. Among these, in order to obtain good elasticity, it is preferable to contain 50% by weight or more of a linear polymer.

  The number average molecular weight of the polymer of component (a-1) is from 3,000 to 50,000, more preferably from 5,000 to 30,000. When the number average molecular weight is less than 3,000, the elastic modulus of the resulting crosslinked rubber becomes high. Conversely, when the number average molecular weight exceeds 50,000, the viscosity tends to be high and the handling of the composition tends to be remarkably reduced. The number average molecular weight can be measured by various methods, but is usually measured by conversion from a terminal group analysis of a polyoxyalkylene polymer or a gel permeation chromatography (GPC) method. The molecular weight of the polyoxyalkylene polymer is the molecular weight converted from the end group analysis.

The alkenyl group in component (a-1) is not particularly limited, and examples thereof include known ones. Among these, an alkenyl group represented by the following general formula (2) is preferable. General formula (2):
^{_{H 2 C = C (R 2}} ) - (2)
(In the formula, R ² is hydrogen or a methyl group.)

  The bonding mode of the alkenyl group to the polyoxyalkylene polymer is not particularly limited, and examples thereof include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond.

As a polymer of the component (a-1), the general formula (3):
_{{H 2 C = C (R} 3) -R 4 -O} a -R 5 (3)
(In the formula, R ³ is hydrogen or a methyl group. R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and one or more ether groups may be contained therein. R ⁵ is an initiator residue of a polyoxyalkylene polymer, and a is a positive integer). R ⁴ described in the general formula (3) is not particularly limited. For example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — and the like can be mentioned. Among these, —CH ₂ — is preferable because synthesis is easy.

Other than the above, the polymer of the component (a-1) is represented by the general formula (4):
_{{H 2 C = C (R} 3) -R 4 -OC (= O)} a -R 5 (4)
(Wherein R ³ , R ⁴ , R ⁵ and a are the same as those in the general formula (3)), and a polymer having an ester bond.

Moreover, general formula (5):
_{{H 2 C = C (R} 3)} a -R 5 (5)
(In formula, R < ³ >, R < ⁵ > and a are the same as the description of General formula (3), (4)), and the polymer shown is also mentioned. Furthermore, the following general formula (6):
_{{H 2 C = C (R} 3) -R 4 -OC (= O) O} a -R 5 (6)
(In the formula, R ³ , R ⁴ , R ⁵ and a are the same as those in the general formulas (3), (4) and (5)), and a polymer having a carbonate bond is also included.

  The polymerization method of the polyoxyalkylene polymer (a-1) is not particularly limited. For example, a normal polymerization method of oxyalkylene disclosed in Japanese Patent Application Laid-Open No. 50-13396 (an anion using caustic alkali) Polymerization method), a polymerization method based on a chain extension reaction method using a polymer obtained by the anionic polymerization method disclosed in JP-A-50-149797 and the like, disclosed in JP-A-7-179597, etc. Porphyrin / aluminum complex catalysts disclosed in JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, and JP-A 61-218632 A polymerization method using a double metal cyanide complex catalyst disclosed in JP-B-46-27250 and JP-B-59-15336 Polymerization method, polymerization method using a catalyst comprising a polyphosphazene salt disclosed in JP-A 10-273512 Patent and the like.

  Among these, a polymerization method using a double metal cyanide complex catalyst is preferable because of its high practicality, easy availability of the catalyst, and stable polymer production. The production method of the double metal cyanide complex catalyst is not particularly limited, and examples thereof include known methods. For example, U.S. Pat. Nos. 3,278,457, 3,278,459, and 5,891,818. 5,767,323, 5,767,323, 5,536,883, 5,482,908, 5,158,922, 4,472,560, 6,063,897, 5,891,818, 5,627,122, 5,482,908, 5,470,813, 5,158,922, etc. The manufacturing method is preferred.

  The method for synthesizing the polyoxyalkylene polymer (a-1) having more than one alkenyl group in one molecule is not particularly limited. For example, a conventional heavy polymer for producing a polyoxyalkylene polymer can be used. In addition to a combination method (anionic polymerization method using caustic alkali) and a chain extension reaction method using this polymer as a raw material, JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, It can be obtained by the methods disclosed in JP-A-61-218632, JP-B-46-27250, JP-B-59-15336 and the like.

  The method for introducing an alkenyl group into the polyoxyalkylene polymer is not particularly limited and includes known methods. For example, a method by copolymerization of a compound having an alkenyl group such as allyl glycidyl ether and an oxyalkylene compound. Can be given. Further, the method for introducing the alkenyl group into the main chain or the side chain is not particularly limited. For example, these functional groups are added to an oxyalkylene polymer having a functional group such as a hydroxyl group or an alkoxide group in the main chain or the side chain. And a method of reacting an organic compound having a functional group and an alkenyl group having reactivity with respect to. A crosslinkable compound containing a polymer in which an alkenyl group is present at the end of the main chain of the polymer is preferable because the resulting cured product has a large effective network chain length and excellent mechanical properties.

  The organic compound having a functional group having reactivity with a functional group such as a hydroxyl group or an alkoxide group and an alkenyl group is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride, and acrylic acid bromide. Acid halides, anhydrides, allyl chloroformates, allyl chlorides, allyl bromides, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, Examples include allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene, and the like.

  The number of alkenyl groups present in one molecule of the polymer as the component (a-1) is preferably more than 1 and not more than 5. When the number of alkenyl groups present in one molecule of the polymer (A) is 1 or less, the curing of the crosslinkable compound tends to be insufficient, and the resulting cured product has an incomplete network structure. There is a tendency that a good molded article cannot be obtained. Moreover, when the alkenyl group which exists in 1 molecule of polymer (a-1) increases, since the network structure of the hardened | cured material obtained becomes too dense, a molded object tends to become hard and brittle. In particular, when the number is 5 or more, the tendency becomes remarkable.

  The number average molecular weight of the component (a-2) of the present invention, which is produced by polymerizing mainly a (meth) acrylic monomer having a main chain having more than one alkenyl group in one molecule, is 3,000 to The main chain of the 50,000 poly (meth) acrylic polymer is produced mainly by polymerizing a (meth) acrylic monomer. Here, “mainly” means that 50 mol% or more of the monomer units constituting the main chain is the above monomer, and preferably 70 mol% or more.

  Among these, from the physical properties of the product, (meth) acrylic acid monomers are preferable, acrylic ester monomers and / or methacrylic ester monomers are more preferable, and acrylic ester monomers are more preferable. Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. 2-methoxybutyl.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  The molecular weight distribution of the poly (meth) acrylic polymer (a-2) in the present invention, that is, the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). / Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1.5 or less, Particularly preferred is 1.4 or less, and most preferred is 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the poly (meth) acrylic polymer (a-2) in the present invention is 3,000 to 50,000, more preferably 5,000 to 30,000. When the number average molecular weight is less than 3,000, the elastic modulus of the resulting crosslinked rubber becomes high. Conversely, when the number average molecular weight exceeds 50,000, the viscosity tends to be high and the handling of the composition tends to be remarkably reduced.

  The poly (meth) acrylic polymer (a-2) in the present invention can be obtained by various polymerization methods, and is not particularly limited. However, radical polymerization methods can be used from the viewpoint of versatility of the monomers and ease of control. Among the radical polymerizations, controlled radical polymerization is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization that allows easy control of the molecular weight and molecular weight distribution of the resulting poly (meth) acrylic polymer (a-2) is more preferred, because of availability of raw materials and ease of introduction of functional groups at the ends of the polymer. Atom transfer radical polymerization is particularly preferred. The radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred to.

  Atom transfer radical polymerization, which is one of preferred methods for synthesizing the poly (meth) acrylic polymer (a-2) in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having more than one alkenyl group in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,

Etc.

  There is no restriction | limiting in particular as a (meth) acrylic-acid type monomer used in atom transfer radical polymerization, All the (meth) acrylic-acid type monomers illustrated above can be used suitably.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses periodic group 7th group, 8th group, 9th group, 10th group, or 11 group element as a central metal, More preferably Examples include transition metal complexes having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067]] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

Although it does not specifically limit as an alkenyl group in (a-2) component, It is preferable that it is what is represented by General formula (7).
H ₂ C═C (R ⁶ ) − (7)
(In the formula, R ⁶ represents hydrogen or an organic group having 1 to 20 carbon atoms.)

The organic group having 1 to 20 carbon atoms of the R ^6, are not particularly limited, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms include preferably Specifically, the following groups are exemplified.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 4 (CH 3)} , - C 6 H 3 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 4 (CH 3), - ( _{CH 2) n -C 6 H 3} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
From the viewpoint of the activity of the hydrosilylation reaction that is the crosslinking reaction of the present invention, R ⁶ is more preferably hydrogen or a methyl group.

  The alkenyl group of the poly (meth) acrylic polymer (a-2) is not particularly limited, but is not activated by a carbonyl group, an alkenyl group or an aromatic ring conjugated with the carbon-carbon double bond. Is preferred.

  The bonding mode between the alkenyl group and the main chain of the poly (meth) acrylic polymer is not particularly limited, but is bonded through a carbon-carbon bond, an ester bond, an ether bond, a carbonate bond, an amide bond, a urethane bond, or the like. It is preferable.

The poly (meth) acrylic polymer (a-2) has more than one alkenyl group in one molecule, and one molecule of poly (meth) acrylic polymer from the viewpoint of the mechanical properties of the cured product. Those having an average of 1.2 to 3.0 are preferred. Although not particularly limited, specifically, the average value obtained by ¹ H-NMR analysis of the number of alkenyl groups introduced per molecule of the poly (meth) acrylic polymer is 1.2 to 3 The number is preferably 0.0, and more preferably 1.5 to 2.5.

  If the cured product obtained from the crosslinkable compound of the present invention is particularly required to have rubber-like properties, the molecular weight between the crosslinking points that greatly affects rubber elasticity can be increased. Therefore, at least one of the alkenyl groups is a molecular chain. It is preferably at the end of the (main chain). More preferably, it has all alkenyl groups at the molecular chain ends.

  The poly (meth) acrylic polymerization having more than one alkenyl group at the molecular end is disclosed in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. It can be manufactured by a method. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of alkenyl groups at the molecular chain ends, while the molecular weight distribution (Mw / Mn) generally has a large value of 2 or more, resulting in a problem of increased viscosity. Therefore, in order to obtain a poly (meth) acrylic polymerization having a narrow molecular weight distribution and a low viscosity and having a high proportion of alkenyl groups at the molecular chain ends, the above-mentioned “living radical weight” is used. It is preferable to use “legal method”.

  As a method for introducing an alkenyl group into the obtained poly (meth) acrylic polymerization, a known method can be used. For example, the method of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0074]-[0099] is mentioned. Among these methods, the diene compound addition method is preferable because it is easier to control. In the case of obtaining from poly (meth) acrylic polymerization containing at least one hydroxyl group in the molecule, a method of reacting alkenyl alcohol at the end of the polymerization (Bb) from the point of easier control, reaction of the polymer It is preferable to use a vinyl polymer containing at least one hydroxyl group in the molecule, which is obtained by the method (Bi) of reacting a terminal with a stabilized carbanion.

  Here, a diene compound addition method, which is one of preferable introduction methods, will be briefly described below. The diene compound addition method is a compound having at least two alkenyl groups with low polymerizability in poly (meth) acrylic polymerization obtained by living radical polymerization of (meth) acrylic monomers (hereinafter referred to as “diene compound”). React.

The alkenyl group of the diene compound includes a terminal alkenyl group [CH ₂ ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, and R ′ is a monovalent or divalent one having 1 to 20 carbon atoms. R and R ′ may be bonded to each other to have a cyclic structure. ] Or an internal alkenyl group [R′—C (R) ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is a monovalent or divalent group having 1 to 20 carbon atoms It is an organic group, and two R or two R ′ may be the same or different from each other. Any two of two R and two R ′ may be bonded to each other to have a cyclic structure. ], But a terminal alkenyl group is more preferable. R is hydrogen or an organic group having 1 to 20 carbon atoms, and examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. The aralkyl group is preferably. Among these, as R, hydrogen or a methyl group is particularly preferable. Examples of the monovalent or divalent organic group having 1 to 20 carbon atoms of R ′ include a monovalent or divalent alkyl group having 1 to 20 carbon atoms, a monovalent or divalent aryl group having 6 to 20 carbon atoms, A monovalent or divalent aralkyl group having 7 to 20 carbon atoms is preferred. Among these, R ′ is particularly preferably a methylene group, an ethylene group, or an isopropylene group. At least two alkenyl groups of the diene compound may be the same or different from each other, and at least two alkenyl groups of the diene compound may be conjugated.

  Specific examples of the diene compound include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, etc. 5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

  Living radical polymerization of (meth) acrylic monomer is performed, and the obtained polymer is isolated from the polymerization system, and then the isolated polymer and the diene compound are subjected to a radical reaction to form an alkenyl group at the target terminal. Although it is possible to obtain poly (meth) acrylic polymerization, it is easy to add a diene compound into the polymerization reaction system at the end of the polymerization reaction or after completion of the reaction of the predetermined (meth) acrylic monomer. More preferred.

  The addition amount of the diene compound may be an equivalent amount or a small excess amount with respect to the polymer growth terminal when the diene compound having a large difference in reactivity between the two alkenyl groups is used. When using a diene compound having the same or little difference in properties, it is preferably an excess amount relative to the polymer growth terminal, specifically preferably 1.5 times or more, more preferably 3 times or more, particularly Preferably it is 5 times or more.

  As the poly (meth) acrylic polymer (a-2) used in the crosslinkable compound of the present invention, among the above-described production methods, those obtained by the following method are particularly suitable.

As a first method, (1a) (meth) acrylic monomers are polymerized by an atom transfer radical polymerization method to obtain the following general formula (8):
^{-C (R 7) (R 8} ) (X) (8)
(Wherein R ⁷ and R ⁸ represent a group bonded to an ethylenically unsaturated group of a (meth) acrylic monomer. X represents chlorine, bromine or iodine). An acrylic polymer is produced, and (2a) the terminal halogen of the polymer is converted into a substituent having an alkenyl group.

  As the second method, (1b) a (meth) acrylic monomer is polymerized by a living radical polymerization method to produce a poly (meth) acrylic polymer, and (2b) the polymer is polymerized. And a method of reacting with a compound having at least two low alkenyl groups.

  As the component (A) in the present invention, these (a-1) polyoxyalkylene polymers having a number average molecular weight of 3,000 to 50,000 having more than one alkenyl group in one molecule, (a- 2) A poly (meth) acrylic polymer having a number average molecular weight of 3,000 to 50,000, which is produced by mainly polymerizing a (meth) acrylic monomer having more than one alkenyl group in one molecule. The polymers may be used alone or in combination. However, in that case, it is necessary to select both components or use a compatibilizing agent so that the (a-1) component and the (a-2) component are uniformly mixed.

  The compound having at least two hydrosilyl groups in one molecule as the component (B) in the present invention is not particularly limited as long as it has a hydrosilyl group, and among these, it is easy to obtain raw materials. An organohydrogenpolysiloxane modified with an organic group is preferred because of its good compatibility with the component A).

  As the organohydrogenpolysiloxane, a known chain or cyclic organohydrogenpolysiloxane can be used, and from the viewpoint of compatibility with the component (A), an aromatic ring-containing chain or cyclic organohydrogen. Siloxane is preferred. Specific examples thereof include hydrosilyl group-containing compounds described in paragraphs [0088] to [0093] of JP-A-2006-291073.

  A linear or cyclic organohydrogenpolysiloxane in which a part of the hydrosilyl group is substituted with a low molecular weight compound having two or more alkenyl groups in the molecule can also be used. Specifically, a modified hydrosilyl group obtained by slowly dropping a low molecular compound having two or more alkenyl groups in the molecule in the presence of a hydrosilylation catalyst described later with respect to an excessive amount of the above hydrosilyl group-containing compound. The containing compound can be used as the hydrosilyl group-containing compound (II). Examples of the low molecular compound having two or more alkenyl groups in the molecule include aliphatic hydrocarbon compounds, ether compounds, ester compounds, carbonate compounds, isocyanurate compounds and aromatic hydrocarbon compounds. Specifically, compounds described in paragraph [0094] of JP-A-2006-291073 can be used. Among such modified hydrosilyl group-containing compounds, the following are considered in consideration of the availability of raw materials, the ease of removal of excessively used hydrosilyl group-containing compounds, and the compatibility with (A). Preferably mentioned.

  The amount of the compound having a hydrosilyl group as the component (B) in the present invention is the amount of the alkenyl group present in the polymer of the component (A) and the amount of the hydrosilyl group present in the compound in the component (B). In relation to the amount, it is appropriately selected, and among these, [total amount of hydrosilyl groups in component (B)] / [total amount of alkenyl groups in component (A)] is preferably 0.5 or more. .7 or more is more preferable. A crosslinkable compound having a [total amount of hydrosilyl groups in component (B)] / [total amount of alkenyl groups in component (A)] of less than 0.5 is low in strength and restorability of the resulting crosslinked rubber, and is adhesive. It becomes difficult to handle. In addition, when [total amount of hydrosilyl groups in component (B)] is excessive compared to [total amount of alkenyl groups in component (A)], a large amount of active hydrosilyl groups are present in the resulting crosslinked rubber. It remains and leads to the occurrence of defects such as voids. Thus, it is necessary to pay attention to both the lower limit and the upper limit for the amount of component (B) used.

  Moreover, in the crosslinkable compound of this invention, the compound which has the said hydrosilyl group may be used only by 1 type, and may be used in mixture of 2 or more types.

The hydrosilylation catalyst which is component (C) of the present invention is not particularly limited, and examples thereof include known ones. For example, solid platinum is supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black and the like. Platinum-vinylsiloxane complex {eg, Pt _X (ViMe ₂ SiOSiMe ₂ Vi) _y , Pt [(MeViSiO) ₄ ] _z }; Platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {for example, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me is a methyl group, Bu is a butyl group, and Vi is a vinyl group) , Ph represents a phenyl group, x, y, z are integers), Pt (acac) ₂ (However, acac represents acetylacetonato), also, Ashby et al., U.S. Patent No. 3 59601 and platinum is disclosed in EP 3159662 - hydrocarbon complexes, and platinum alcoholate catalysts may also be mentioned that disclosed in Lamoreaux et al. U.S. Pat. No. 3,220,972.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl _{4 and the} like.

These catalysts may be used alone or in combination. Among the above catalysts, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) _{2 and the} like are preferable because of their high catalytic activity.

  Although there is no restriction | limiting in particular as the usage-amount of a catalyst (C), since the light-color type electroconductive metal oxide which is (D) of this invention can act as an inhibitor with respect to hydrosilylation reaction, it is practical hardening. In order to ensure the property, the concentration of the metal atom in the component (C) in the crosslinkable compound of the present invention is preferably 10 ppm or more. On the other hand, a crosslinkable compound using an amount exceeding 1000 ppm tends to make it difficult to ensure pot life.

The light-colored conductive metal oxide which is the component (D) of the present invention imparts conductivity to the crosslinkable compound of the present invention. In addition, since the metal oxide is light-colored, the resulting crosslinked rubber can be colored by adding a pigment or the like to the crosslinkable compound of the present invention. A typical example of such a light-colored conductive metal oxide is a metal oxide surface-treated with a conductive material, and more specifically, a surface treatment with tin oxide doped with antimony. Examples thereof include titanium oxide, potassium titanate surface-treated with tin oxide doped with antimony, and zinc oxide surface-treated with aluminum.
Here, the light color system means a light color such as white, gray, light blue, mauve, pink, or skin color.

These components (D) are used so that the resulting crosslinked rubber has a surface resistance of 10 ⁹ Ω / □ or less, or a volume resistivity of 10 ⁹ Ω · cm or less.

  The amount of component (D) used is such that the volume fraction of component (D) in the crosslinkable compound of the present invention is 5% or more. When the volume fraction is less than 5%, the surface resistance value and the volume resistivity of the crosslinked rubber obtained from the crosslinkable compound of the present invention are not sufficiently lowered. On the other hand, when the volume fraction exceeds 50%, the viscosity of the crosslinkable compound of the present invention is high and the workability is deteriorated.

  The light-colored filler which is the component (E) of the present invention is used for various purposes such as increasing the mechanical strength of the crosslinked rubber obtained from the crosslinkable compound of the present invention, imparting flame retardancy, and reducing costs.

  Examples of such light-colored fillers include inorganic fillers such as silica, clay, talc, calcium carbonate, aluminum oxide, magnesium hydroxide, titanium oxide, and magnesium oxide.

Moreover, since the particle size of the light-colored conductive metal oxide which is the component (D) of the present invention is relatively large, the reinforcing effect cannot be expected so much. In such a case, it is preferable to use finely powdered silica that can be expected to have a reinforcing effect due to its addition in a small amount.
The amount of component (E) used is 1 to 300 parts by weight, preferably 5 to 200 parts by weight, per 100 parts by weight of component (A) of the present invention. When the usage-amount of these components is too small, the expectation effect by providing (E) component will not fully express. On the other hand, when the amount of these components used is too large, the resulting crosslinkable compound has a high viscosity, making it difficult to handle.

  Moreover, a storage stability improving agent can be added to the crosslinkable compound containing the components (A) to (D) or the components (A) to (E) of the present invention, if necessary. The storage stability improver serves to prevent deterioration of physical properties such as curing and deterioration during storage of the crosslinkable compound. The storage stability improver is not particularly limited as long as it is a known stabilizer known as a storage stabilizer of the component (B) of the present invention and achieves the intended purpose. Examples thereof include compounds containing a group unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. Specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole, vitamin E, 2- (4-morphodinyldithio) benzothiazole, 3-methyl-1-buten-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyl-3-ol Diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene, and the like.

  In addition, the crosslinkable compound containing the components (A) to (D) or the components (A) to (E) of the present invention includes various fillers, antioxidants, ultraviolet absorbers, pigments, if necessary. A surfactant, a plasticizer, a solvent, and a silicon compound may be appropriately added.

  The method for obtaining the crosslinkable compound of the present invention is not particularly limited. For example, the components (A) to (D), or the components (A) to (E), and various additives and fillings used as necessary. Examples thereof include a method of mixing the agent using a rotary mixer such as a planetary mixer or a biaxial disperser, a kneader, a bumper mixer, a roll or the like. Here, it is desirable to uniformly disperse and stabilize the component (B) in the component (A) and to remove moisture contained in the crosslinkable compound as much as possible. If the dispersion of the component (B) in the component (A) is uneven or unstable, the properties of the crosslinkable compound tend to change greatly with time during storage. Moreover, when there is much water | moisture content in a crosslinkable compound, there exists a tendency for it to foam by reacting (B) component and a water | moisture content at the time of hardening reaction, and to produce a void in crosslinked rubber.

  The method for obtaining a polyoxyalkylene-based, poly (meth) acrylic-based, or polyoxyalkylene-poly (meth) acrylic-based crosslinked rubber from the crosslinkable compound of the present invention is not particularly limited and is generally used. The same method as that for the thermosetting liquid rubber can be employed. It is possible to apply a method for obtaining a rubber molded body, such as coating, injection, screen printing, etc., and the same handling as an adhesive or potting agent, press molding, injection molding, transfer molding, extrusion molding or the like.

  Further, as a method for obtaining a rubber molded body with high productivity from a thermosetting type crosslinkable compound having fluidity at room temperature, liquid injection molding known as liquid silicone rubber is known. The crosslinkable compound can also be applied to this liquid injection molding.

  Moreover, in these various handling methods, the crosslinkable compound of the present invention can be handled as a one-component form including all components, or two components can be mixed so that the components (B) and (C) are not mixed. It is also possible to treat it as a two-liquid form distributed to each other. In the former case, since the reaction can proceed gradually even at room temperature, storage at a low temperature is required, but the trouble of mixing two liquids at the time of molding can be omitted. In the latter case, it is necessary to devise so that the two liquids can be mixed at the time of molding, and can be applied, filled and injected in a state that does not contain bubbles, but it is advantageous for long-term storage of the crosslinkable compound. . For handling such two-component liquid crosslinkable compounds, it is used for two-component mixing and discharging devices used in liquid injection molding systems developed for liquid silicone, two-component urethane resins, and epoxy resins. The two-component mixing / discharging device that has been used can be used.

  The semiconductive crosslinked rubber thus obtained from the semiconductive crosslinkable compound of the present invention has less risk of dust adhesion and discharge breakdown due to static electricity, and various electronic / electric product parts and their manufacture. It can be widely used in processes, semiconductor manufacturing processes, and the like.

  More specifically, it is various rubber parts used for the purpose of vibration / shock absorbing function, fixing or temporary fixing function such as adhesion and adhesion, sealing function such as waterproof, dustproof and airtight.

  Next, the semiconductive crosslinkable compound of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Production Example 1)
Polymerization of propylene oxide using polyoxypropylene diol having a number average molecular weight of 2,000 as an initiator and a composite metal cyanide complex catalyst results in a number average molecular weight of about 10,000 (analysis of terminal hydroxyl group and allyl group) Of polyoxypropylene diol). After adding a 28% methanol solution of sodium methylate equivalent to 1.2 equivalents of the hydroxyl group of the polyoxypropylenediol, devolatilization was performed at 130 ° C. until no methanol was recovered. Next, after allyl chloride was added and reacted, unreacted allyl chloride was removed by devolatilization under reduced pressure. Then, it refine | purified with hexane and water, and obtained the polyoxyalkylene type polymer (A-1) which has about two allyl terminals in 1 molecule. This polymer (A-1) was a pale yellow liquid with a viscosity of 7 Pa · s, and the allyl content determined from the iodine valence was 0.22 mmol / g.

(Production Example 2)
Table 1 shows the amount of each raw material used.
(1) Polymerization process The inside of the stainless steel reaction vessel with a stirrer was deoxygenated, cuprous bromide and a part of the total acrylic ester were charged, and the mixture was heated and stirred. Acetonitrile (described as polymerization acetonitrile in Table 1) as a polymerization reaction solvent, diethyl 2,5-dibromoadipate as an initiator was added and mixed, and pentamethyldiethylenetriamine (hereinafter referred to as “the temperature of the mixture” was adjusted to about 80 ° C.) , Abbreviated as triamine), and the polymerization reaction was started. The remaining acrylic ester was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature increases due to the heat of polymerization, so the internal temperature was adjusted to about 80 ° C to about 90 ° C. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, the unreacted monomer and acetonitrile for polymerization were removed by devolatilization under reduced pressure to obtain a polymer concentrate.
(2) Diene reaction step 1,7-octadiene (hereinafter abbreviated as diene or octadiene) and acetonitrile (described as diene reaction acetonitrile in Table 1) as a diene reaction solvent are added to the concentrate, and a triamine (diene in Table 1). The diene reaction was started by adding triamine for reaction). While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. The reaction solution was markedly colored by the polymerization catalyst used.
(3) Oxygen treatment step When the diene reaction was completed, an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
(4) First rough purification step Butyl acetate was used as a diluent solvent for the polymer. The concentrate was diluted with about 100 to 150 parts by weight of butyl acetate with respect to the polymer, a filter aid was added and stirred, and then insoluble catalyst components were removed by filtration. The filtrate was colored by the polymerization catalyst residue and was turbid.
(5) Second rough purification step The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and aluminum silicate (KYOWARD 700SEN: manufactured by Kyowa Chemical) and hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical) were added as adsorbents. . After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for 1 hour, insoluble components such as an adsorbent were removed by filtration. A clear filtrate with coloration was obtained. The filtrate was concentrated to obtain a crude polymer product.
(6) Dehalogenation process (high-temperature heat treatment process) / adsorption purification process Crude polymer purified product, heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), part of the adsorbent (KYOWARD 700SEN, KYOWARD) 500SH), heated under stirring under reduced pressure, and heated and stirred, heated and stirred for about several hours at a high temperature of about 170 ° C. to about 200 ° C., and evacuated under reduced pressure to eliminate the halogen group in the polymer. Adsorption purification was performed. Add the remaining adsorbent (KYOWARD 700SEN, KYOWARD 500SH), add about 10 parts by weight of butyl acetate (new product: acid value 2.3 mmol KOH / kg) as a diluent solvent to the gas phase part. Was mixed with an oxygen-nitrogen mixed gas atmosphere, and further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for several hours to continue the adsorption purification. The treatment liquid was further diluted with 90 parts by weight of butyl acetate with respect to the polymer, and filtered to remove the adsorbent. The filtrate was concentrated to collect butyl acetate as a dilution solvent, and a polymer having alkenyl groups at both ends was obtained.
Table 1 shows the number of alkenyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

“Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804, shodex GPC K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used. The functional group introduced per polymer molecule was subjected to functional group concentration analysis (solvent: deuterated chloroform, measurement temperature: 23 ° C.) by ¹ H-NMR (400 MHz), and calculated from the number average molecular weight determined by GPC.

(Production Example 3)
One molecule is obtained by adding 0.2 equivalent of α-methylstyrene of the total amount of hydrosilyl groups in the presence of a platinum catalyst to methylhydrogen silicone having 7.5 repeating units represented by (—Si—O—) on average. A compound (B-1) having an average of 6 hydrosilyl groups therein was obtained. The Si—H group content of this compound determined from the amount of hydrogen generated by treating the SiH group in the obtained compound (B-1) with an alkaline aqueous solution was 8.1 mmol / g.

(Production Example 4)
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene of the total hydrosilyl group amount is added to methylhydrogen silicone having an average of 10 repeating units represented by (—Si—O—), A compound (B-2) having an average of 5 hydrosilyl groups was obtained. The Si—H group content of this compound determined from the amount of hydrogen generated by treating the SiH group in the obtained compound (B-2) with an aqueous alkaline solution was 3.8 mmol / g.

(Examples 1-6 and Comparative Examples 1-3)
According to the blending amount shown in Table 2, the allyl group-terminated polyoxyalkylene polymer (A-1) obtained in Production Example 1 or the allyl group-terminated polyacrylic polymer obtained in Production Example 2 and the component (D) Titanium oxide coated with tin oxide doped with antimony (manufactured by Titanium Industry Co., EC-210), zinc oxide doped with aluminum (manufactured by Hux Itec Corp., 23-K), hindered phenol antioxidant (Ciba・ Ilganox 245 manufactured by Specialty Chemical Co., Ltd. In some examples, fine powder silica (bulk specific gravity 70 g / l) was kneaded with a roll as component (E). Subsequently, the hydrosilyl compound (B-1, 2), platinum vinylsiloxane (3% platinum xylene solution), and acetylene alcohol (Shinfin Chemical Co., Surfinol 61) are mixed as the component (B) to the obtained mixture. did. In Comparative Examples 1 and 3, component (D) was not used.

  After defoaming the composition thus obtained, a 2 mm thick cured product sheet was obtained by hot press molding at 150 ° C. for 3 minutes using a 2 mm thick spacer and two press plates. It was. The obtained sheet was further heat-treated with a 150 ° C. hot air dryer for 1 hour.

  The resulting cured sheet was measured for volume resistivity and surface resistance according to the method of Japan Rubber Association Standard SRIS 2304. These results are shown in Table 2.

Moreover, the JIS 2 (2/3) type dumbbell test piece was punched out, and the breaking strength and breaking elongation were measured based on the tensile test described in JIS K 6251. The obtained results are shown in Table 2.
In addition, all the hardened | cured material sheets obtained by Examples 1-6 were white or light gray.

Claims (15)

The surface resistance value measured by the method of SRIS 2304 of the crosslinked rubber obtained by curing the components (A) to (D) as essential components is 10 ⁹ Ω / □ or less, or the volume resistivity value is 10 ⁹ Ω · cm. A semiconductive crosslinkable compound characterized in that:
(A) (a-1) a polyoxyalkylene polymer having a number average molecular weight of 3,000 to 50,000 having an average of more than one alkenyl group in one molecule, (a-2) an average in one molecule At least an average of at least one polymer (B) having at least one alkenyl group selected from the group consisting of a poly (meth) acrylic polymer having a number average molecular weight of 3,000 to 50,000. Compound having two hydrosilyl groups (C) Hydrosilylation catalyst (D) Light color conductive metal oxide The semiconductive crosslinkable compound according to claim 1, wherein the light-colored conductive metal oxide as component (D) is a metal oxide surface-treated with a conductive material. The light-colored conductive metal oxide as component (D) is surface-treated with titanium oxide surface-treated with antimony-doped tin oxide, potassium titanate surface-treated with antimony-doped tin oxide, and aluminum. The semiconductive crosslinkable compound according to claim 1, which is at least one selected from the group consisting of zinc oxide. (A) The component is (a-1), and the volume fraction that occupies the semiconductive crosslinkable compound having the (A) component to the (D) component as essential components of the conductive filler that is the (D) component is The semiconductive crosslinkable compound according to any one of claims 1 to 3, wherein the content is 5% or more. (A) The component is (a-2), and the volume fraction of the conductive filler that is the component (D) accounts for the semiconductive crosslinkable compound having the components (A) to (D) as essential components. The semiconductive crosslinkable compound according to any one of claims 1 to 3, which is 10% or more. The semiconductive crosslinkable compound according to any one of claims 1 to 5, wherein a light-colored filler is an essential component as the component (E). The semiconductive crosslinkable compound according to claim 6, wherein the light-colored filler as component (E) is finely divided silica. The semiconductive crosslinkable compound according to any one of claims 1 to 7, wherein the hydrosilylation catalyst as component (C) is a platinum complex compound, and the platinum concentration is 10 ppm or more of the whole. The (a-2) component poly (meth) acrylic polymer is composed of ethyl acrylate, butyl acrylate, 2-methoxyethyl acrylate, 2-methoxybutyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. The semiconductive crosslinkable compound according to claim 1, comprising at least one monomer unit selected from the group consisting of: The semiconductive crosslinkability according to any one of claims 1 to 9, wherein the main chain of the poly (meth) acrylic polymer as the component (a-2) is produced by a living radical polymerization method. compound. The semiconductive crosslinkable compound according to any one of claims 1 to 10, wherein the component (B) is an organohydrogenpolysiloxane having an average of at least two hydrosilyl groups in one molecule. . A semiconductive crosslinked rubber obtained from the semiconductive crosslinkable compound according to any one of claims 1 to 11. A semiconductive crosslinked rubber obtained from the semiconductive crosslinkable compound according to any one of claims 1 to 11 and used for the purpose of vibration and shock absorption. The semiconductive crosslinked rubber used for the purpose of fixation and / or temporary fixation obtained from the semiconductive crosslinkable compound according to any one of claims 1 to 11. The semiconductive crosslinked rubber used for the purpose of the seal | sticker obtained from the semiconductive crosslinkable compound of any one of Claims 1-11.