JP4786216B2 - Crosslinkable polymer composition and use thereof - Google Patents

Description

  The present invention relates to a crosslinkable (vulcanizable) polymer composition and use thereof, and more particularly to a crosslinkable polymer composition and use thereof which can obtain a cross-linked molded article having excellent transparency and weather resistance.

  Compositions based on hydrocarbon rubbers such as ethylene / α-olefin / non-conjugated polyene copolymers are widely used, but in the prior art, the transparency is at the same level as polyvinyl chloride. It was not reached.

  Patent Document 1 discloses a vulcanized rubber composition having improved transparency. However, in applications that require transparency, there are many applications that require a good appearance (hue), and weather resistance (transparency, no change in appearance) may also be required. The material described in Patent Document 1 has room for improvement.

  Patent Document 2 discloses a method for adding a weather stabilizer for improving the weather resistance of an ethylene / α-olefin / non-conjugated polyene copolymer rubber composition. However, the addition of weather stabilizers often does not lead to an essential solution, and the weather stabilizers may have another adverse effect, so they are excellent in weather resistance stability even when no weather stability is added. A desirable composition is desirable.

Furthermore, Patent Document 3 discloses a method for crosslinking a special EPT using a hydrosilylation reaction, which describes that it has excellent heat aging resistance and can be hot-air crosslinked. However, this document does not specifically disclose making the vulcanized rubber transparent. Moreover, it does not describe about weather resistance.
JP 2002-146132 A JP 2003-301080 A International publication 00/55251 pamphlet

  The present invention is intended to solve the problems associated with the prior art as described above, and is obtained from a crosslinkable polymer composition capable of obtaining a crosslinked molded article having excellent transparency and weather resistance, and the composition. The object is to provide a crosslinked molded article.

  The crosslinkable polymer composition according to the present invention comprises an organic polymer (A) having an alkenyl group, a SiH group-containing compound (B) having at least two SiH groups in one molecule, an ethylene / polar monomer copolymer. It is characterized by containing a polymer (C).

  The organic polymer (A) is preferably an ethylene / α-olefin / non-conjugated polyene random copolymer in which the non-conjugated polyene is at least one of the following general formula (I) or (II).

Wherein n is an integer from 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ),

(Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
The ethylene / α-olefin / non-conjugated polyene random copolymer is:
(I) The molar ratio (ethylene unit / α-olefin unit) of the ethylene unit and the α-olefin unit having 3 to 20 carbon atoms is in the range of 60/40 to 85/15,
(Ii) the iodine value is in the range of 0.5-30 g / 100 g;
(Iii) The intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is in the range of 0.3 to 3.0 dl / g,
(Iv) The branching index determined from the dynamic viscoelasticity measuring instrument is preferably 5 or more.

The refractive index of the ethylene / polar monomer copolymer (C) is preferably in the range of 1.470 to 1.490.
The crosslinkable polymer composition comprises 0.1 to 100 parts by weight of the SiH group-containing compound (B) and 100 parts by weight of the ethylene / polar monomer copolymer (C) with respect to 100 parts by weight of the organic polymer (A). It is preferable to contain 1-150 weight part.

The crosslinkable polymer composition according to the present invention may further contain at least one compounding agent selected from a catalyst (D), a reaction inhibitor (E) and silica (F).
The catalyst (D) is preferably a platinum-vinylsiloxane complex.

The molded body according to the present invention is obtained by crosslinking the crosslinkable polymer composition.
Formed bodies according to the present invention include electrical / insulating parts, industrial parts, and the like.

With the crosslinkable polymer composition of the present invention, a crosslinked molded article having excellent transparency and weather resistance can be obtained. Further, since it can be continuously vulcanized under hot air, it is excellent in terms of the production cost of the crosslinked molded article.
The crosslinked molded article according to the present invention is excellent in transparency and weather resistance.

Hereinafter, the crosslinkable (vulcanizable) polymer composition according to the present invention and its use will be described in detail.
The crosslinkable polymer composition according to the present invention comprises an organic polymer (A) having an alkenyl group, a SiH group-containing compound (B) having at least two SiH groups in one molecule, an ethylene / polar monomer copolymer. It is a composition containing a polymer (C).

First, each component which forms the crosslinkable polymer composition according to the present invention will be described.
Organic polymer containing alkenyl group (A)
The organic polymer (A) containing an alkenyl group used in the present invention is not particularly limited as long as it is an organic polymer containing at least one alkenyl group in the molecule, and organic polymers having various main chain skeletons. Coalescence can be used. In this specification, the term “polymer” of the organic polymer (A) includes both a homopolymer and a copolymer.

As such an organic polymer (A), specifically,
Polyether polymers such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer;
A condensate of a dibasic acid such as terephthalic acid, isophthalic acid or adipic acid or an acid anhydride thereof with a glycol such as ethylene glycol, propylene glycol or neopentyl glycol;
Polyester copolymers obtained by ring-opening polymerization of lactones;
Ethylene / α-olefin / non-conjugated polyene random copolymer (A2) containing alkenyl group, ethylene / α-olefin random copolymer rubber, polyisobutylene, copolymer of isobutylene and isopropylene, polychloroprene, Polyisoprene, copolymers of isoprene and butadiene, acrylonitrile or styrene, polybutadiene, copolymers of butadiene and styrene or acrylonitrile, and polyisoprene, polybutadiene, isoprene, copolymers of butadiene and acrylonitrile, styrene, etc. A hydrocarbon polymer (A1) such as a copolymer obtained by hydrogenating the polymer;
Acrylic acid ester polymers of polyacrylic acid esters obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, acrylic acid esters such as ethyl acrylate and butyl acrylate, and vinyl acetate, acrylonitrile, methyl methacrylate, styrene, and the like;
A graft polymer obtained by polymerizing a vinyl monomer in the organic polymer;
Polysulfide polymer;
Examples thereof include polycarbonate polymers produced by condensation polymerization of bisphenol A and carbonyl chloride.

  Among these, a polyester polymer, a polyether polymer, an acrylate polymer, and a hydrocarbon polymer (A1) are preferable. Of these, the hydrocarbon polymer (A1) is more preferable. Among the hydrocarbon polymers (A1), ethylene / α-olefin / non-conjugated polyene random copolymer (A2) containing an alkenyl group, ethylene / α-olefin random copolymer rubber, and polyisobutylene are particularly preferable. .

As the alkenyl group, an alkylidene group and a vinyl group are preferable.
As a method of introducing an alkenyl group, a method of introducing it during polymerization or a method of introducing it after polymerization can be considered. Such methods are well known.

  Among these organic polymers containing alkenyl groups, ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene represented by the following general formula (I) or (II) are particularly preferred. An ethylene / α-olefin / non-conjugated polyene random copolymer which is a polymer is preferred.

Specific examples of such α-olefins having 3 to 20 carbon atoms include propylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1- Examples include pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

These α-olefins are used alone or in combination of two or more.
The non-conjugated polyene is a vinyl group-containing norbornene compound represented by the following general formula (I) or (II).

In general formula (I), n is an integer of 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. N-pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Specific examples of the alkyl group having 1 to 5 carbon atoms represented by R ² include alkyl groups having 1 to 5 carbon atoms among the specific examples of R ¹ described above.

In the general formula (II), R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ³ include the same alkyl groups as the specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ .

Specific examples of the norbornene compound represented by the general formula (I) or (II) include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, and 5- (2-propenyl) -2-norbornene. 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3- Butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,
3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5- Hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2
-Norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- ( 1,2-dimethyl-5-hexyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene Etc. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These norbornene compounds can be used alone or in combination of two or more.

In the present invention, in addition to the norbornene compound, the following non-conjugated polyene can be used in combination as long as the physical properties of the present invention are not impaired.
Specific examples of such a non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Chain non-conjugated dienes such as 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene , Cyclic non-conjugated dienes such as dicyclopentadiene;
Trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like can be mentioned.

The ethylene / α-olefin / non-conjugated polyene random copolymer comprising the above components preferably has the following characteristics.
(I) Molar ratio of ethylene unit to α-olefin unit having 3 to 20 carbon atoms The ethylene / α-olefin / non-conjugated polyene random copolymer is composed of units derived from ethylene and 3 to 20 carbon atoms. The molar ratio (ethylene unit / α-olefin unit) to units derived from an α-olefin (hereinafter sometimes simply referred to as “α-olefin”) is 50/50 to 85/15, preferably 50/50. -80/20, preferably 55/45 to 70/30, particularly preferably 55/45 to 65/35.
When this molar ratio is within the above range, a polymer composition capable of providing a crosslinked molded article having excellent weather resistance and transparency can be obtained.
(Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer is 0.5 to 30 (g / 100 g), preferably 0.8 to 25 (g / 100 g), more preferably. 1 to 20 (g / 100 g), particularly preferably 1.5 to 15 (g / 100 g), more preferably 2 to 10 (g / 100 g), most preferably 2 to 6 (g / 100 g). .
When the iodine value is within the above range, a polymer composition having high crosslinking efficiency is obtained, and a polymer composition capable of providing a crosslinked molded article having excellent weather resistance is obtained. An iodine value exceeding 30 is not preferable because it is disadvantageous in cost.
(Iii) Intrinsic viscosity The intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene random copolymer measured in decalin at 135 ° C. is 0.1 to 3.0 dl / g, preferably 0.1 to 2. 0.8 dl / g, more preferably 0.5 to 2.5 dl / g, still more preferably 0.8 to 2.3 dl / g, and particularly preferably 1.0 to 2.0 dl / g.
When the intrinsic viscosity [η] is within the above range, a polymer composition that can provide a crosslinked molded article having excellent weather resistance and excellent workability and strength characteristics can be obtained.
(Iv) Branching index determined from a dynamic viscoelasticity measuring device The branching index determined from a dynamic viscoelasticity measuring device of ethylene / α-olefin / non-conjugated polyene random copolymer is preferably 5 or more, preferably 7 or more, More preferably, it is 9 or more, Most preferably, it is 10 or more. When this branching index value is smaller than 5, the viscosity in the high shear rate region is increased and the fluidity is deteriorated, so that the roll processability and the extrusion processability are deteriorated.

The ethylene / α-olefin / non-conjugated polyene random copolymer preferably further has the following characteristics.
(V) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer measured by GPC is 3 to 50, preferably 3.3 to 40, more preferably 3.5 to 30, most preferably. Is 10-30.
When the molecular weight distribution (Mw / Mn) is within the above range, a polymer composition that can provide a crosslinked molded article having excellent processability and excellent strength characteristics is obtained.

The ethylene / α-olefin / non-conjugated polyene random copolymer used in the present invention has, for example, a polymerization temperature of 30 to 30 in the presence of a catalyst containing the following vanadium compound (a) and organoaluminum compound (b) as main components. 60 ° C., particularly 30 to 50 ° C., polymerization pressure 4 to 12 kgf / cm ² , especially 5 to 8 kgf / cm ² , molar ratio of non-conjugated polyene and ethylene supplied (non-conjugated polyene / ethylene) 0.01 to 0 .2 is obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a vinyl group-containing norbornene compound represented by the above general formula (I) or (II). The copolymerization is preferably carried out in a hydrocarbon medium.

Examples of the vanadium compound (a) include VO (OR) _n X _3-n
(In the formula, R is a hydrocarbon group, X is a halogen atom, and n is an integer of 0 or 1 to 3).
Or a vanadium compound represented by VX ₄ (X is a halogen atom).

The soluble vanadium compound is a component that is soluble in the hydrocarbon medium of the polymerization reaction system, and more specifically,
General formula VO (OR) _a X _b or V (OR) _c X _d
(Wherein R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4)
The vanadium compound represented by these, or these electron donor adducts can be mentioned as a representative example.

More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO
(O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₃
, VCl ₄ , VOCl ₃ , VO (On-C ₄ H ₉ ) ₃ , VCl ₃ .2OC ₆ H ₁₂ OH, and the like.

As the organoaluminum compound (b),
R _'m AlX' _3-m
(R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is an integer of 1 to 3)
The organoaluminum compound represented by these is mentioned.

As the organoaluminum compound (b), specifically,
Trialkylaluminums such as triethylaluminum, tributylaluminum, triisopropylaluminum;
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by R ¹ _0.5 Al (OR ¹ ) _0.5 or the like;
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide;
Partially halogenated alkyl aluminums such as alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide ;
Partially hydrogenated alkylaluminums such as dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

In the present invention, among the vanadium compound (a), the soluble vanadium compound represented by VOCl ₃ and the organoaluminum compound (b), Al (OC ₂ H ₅ ) ₂ C
When a blend of 1 / Al ₂ (OC ₂ H ₅ ) ₃ Cl ₃ (blend ratio is 1/5 or more) is used as a catalyst component, Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) Since an ethylene / α-olefin / non-conjugated polyene random copolymer having a later insoluble content of 1% or less is obtained, it is preferable.

Further, as the catalyst used in the copolymerization, a so-called metallocene catalyst, for example, a metallocene catalyst described in JP-A-9-40586 may be used.
Further, the ethylene / α-olefin / non-conjugated polyene random copolymer used in the present invention may be graft-modified with a polar monomer such as an unsaturated carboxylic acid or a derivative thereof (for example, an acid anhydride or ester).

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo [2.
2.1] hept-2-ene-5,6-dicarboxylic acid and the like.

Specific examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6- And dicarboxylic acid anhydride. Among these, maleic anhydride is preferable.

Specific examples of the unsaturated carboxylic acid ester include methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, and bicyclo [2. 2.1] dimethyl hept-2-ene-5,6-dicarboxylate and the like. Among these, methyl acrylate and ethyl acrylate are preferable.

  The above-mentioned graft modifiers (graft monomers) such as unsaturated carboxylic acids are used singly or in combination of two or more. In any case, the above-mentioned ethylene / α-olefin / nonconjugated polyene before graft modification is used. The graft amount is preferably 0.1 mol or less per 100 g of the copolymer.

  Use of an ethylene / α-olefin / non-conjugated polyene random copolymer having the graft amount within the above range can provide a cross-linked molded article having excellent cold resistance, and excellent fluidity (molding processability). A polymer composition is obtained.

  The graft-modified ethylene / α-olefin / nonconjugated polyene random copolymer comprises the above-mentioned unmodified ethylene / α-olefin / nonconjugated polyene copolymer and an unsaturated carboxylic acid or a derivative thereof as a radical initiator. It can be obtained by reacting in the presence.

  This grafting reaction can be performed as a solution or in a molten state. When the graft reaction is performed in a molten state, it is most efficient and preferable to perform it continuously in an extruder.

Specific examples of the radical initiator used in the graft reaction include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butyl. Cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, 2,
Dialkyl peroxides such as 5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene;
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di -Peroxyesters such as t-butylperoxyphthalate;
Ketone peroxides such as dicyclohexanone peroxide;
And a mixture thereof. Among them, organic peroxides having a half-life of 1 minute at a temperature in the range of 130 to 200 ° C. are preferable, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3. Organic peroxides such as 1,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide and t-butyl hydroperoxide are preferred.

  Examples of polar monomers other than unsaturated carboxylic acids or derivatives thereof (eg, acid anhydrides and esters) include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, Aromatic vinyl compounds, vinyl ester compounds, vinyl chloride and the like can be mentioned.

SiH group-containing compound (B)
The SiH group-containing compound (B) used in the present invention reacts with the organic polymer (A) and acts as a crosslinking agent. The molecular structure of the SiH group-containing compound (B) is not particularly limited, and it can be used for conventionally produced resinous materials such as linear, cyclic, branched structures, or three-dimensional network structures. It is necessary that one molecule contains at least 2, preferably 3 or more hydrogen atoms directly bonded to silicon atoms, that is, SiH groups.

Such SiH group-containing compound (B) is usually represented by the following general composition formula R ⁴ _b H _c SiO _{(4-bc) / 2}
The compound represented by these can be used.

In the above general composition formula, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms (excluding those having an aliphatic unsaturated bond). Examples of such a monovalent hydrocarbon group include a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group, in addition to the alkyl group having 1 to 10 carbon atoms exemplified as R ^1. it can. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

  Further, b is 0 ≦ b <3, preferably 0.6 <b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 0 <c ≦ 3, preferably 0.002. ≦ c <2, particularly preferably 0.01 ≦ c ≦ 1, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7.

This SiH group-containing compound (B) is an organohydrogenpolysiloxane having preferably 2 to 1000, particularly preferably 2 to 300, and most preferably 4 to 200 silicon atoms in one molecule. In terms of
Siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane;
Molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-blocked methylhydrogenpolysiloxane, both ends of molecular chain Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends dimethylhydro Gensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, comprising R ⁴ ₂ (H) SiO _1/2 units and SiO _4/2 units, optionally R ⁴ ₃ SiO _1/2 units, R ⁴ ₂ S Mention may be made of silicone resins which may contain iO _2/2 units, R ⁴ (H) SiO _2/2 units, (H) SiO _3/2 or R ⁴ SiO _3/2 units.

Examples of the methylhydrogenpolysiloxane blocked with a trimethylsiloxy group at both ends of the molecular chain include, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group. And the like.
(CH ₃ ) ₃ SiO — (— SiH (CH ₃ ) —O—) _d —Si (CH ₃ ) ₃
(D in the formula is an integer of 2 or more.)
As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy group at both ends of the molecular chain, a compound represented by the following formula, and further, in the following formula, part or all of the methyl group is ethyl group, propyl group, phenyl group, Examples include compounds substituted with a trifluoropropyl group and the like.
(CH ₃ ) ₃ SiO — (— Si (CH ₃ ) ₂ —O—) _e — (— SiH (CH ₃ ) —O—) _f —Si (CH ₃ ) ₃
(In the formula, e is an integer of 1 or more, and f is an integer of 2 or more.)
Examples of the methyl hydrogen polysiloxane blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following formula, and further, part or all of the methyl group in the following formula: ethyl group, propyl group, phenyl group, trifluoropropyl group, etc. And the like.
HOSi (CH ₃ ) ₂ O — (— SiH (CH ₃ ) —O—) ₂ —Si (CH ₃ ) ₂ OH
As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with silanol groups at both ends of the molecular chain, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is ethyl group, propyl group, phenyl group, Examples include compounds substituted with a trifluoropropyl group and the like.

_{HOSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH (e in the formula 1 or more And f is an integer of 2 or more.)
Examples of the dimethylpolysiloxane blocked with dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is ethyl group, propyl group, phenyl group, trifluoropropyl group. And the like.

HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) _e —Si (CH ₃ ) ₂ H
(E in the formula is an integer of 1 or more.)
Examples of the dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane having both molecular chain ends include, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is ethyl, propyl, phenyl, trifluoro Examples thereof include compounds substituted with a propyl group or the like.

HSi (CH ₃ ) ₂ O — (— SiH (CH ₃ ) —O—) _e —Si (CH ₃ ) ₂ H
(E in the formula is an integer of 1 or more.)
Examples of dimethylsiloxane / methylhydrogensiloxane copolymers blocked with dimethylhydrogensiloxy groups at both ends of the molecular chain include, for example, compounds represented by the following formula, and further, in the following formula, a part or all of the methyl groups are ethyl, propyl, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H
(In the formula, e and h are each an integer of 1 or more.)
Such a compound can be produced by a known method, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane, and hexamethyldisiloxane or 1,3-dihydro-1,1 which can be a terminal group. And a compound containing a triorganosilyl group or a diorganohydrogensiloxy group, such as 1,3,3-tetramethyldisiloxane, at −10 ° C. in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid. It can be easily obtained by equilibrating at a temperature of about ~ 40 ° C.

  The SiH group-containing compound (B) is 0.1 to 50 parts by weight, preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the organic polymer (A). More preferably, it is used in a proportion of 0.2 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, and most preferably 0.5 to 5 parts by weight. When the SiH group-containing compound (B) is used in a proportion within the above range, a polymer composition capable of forming a crosslinked molded article having excellent transparency and weather resistance can be obtained.

  Further, the ratio of SiH groups to aliphatic unsaturated groups involved in the crosslinking of the organic polymer (A) (SiH group / aliphatic unsaturated group) is 0.2 to 10, more preferably 0.5 to 2, particularly It is preferable that it is 0.7-1.2.

Ethylene / polar monomer copolymer (C)
The ethylene / polar monomer copolymer (C) used in the present invention is a copolymer of ethylene and the following polar monomer.

Specific examples of polar monomers include α such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid. , β-unsaturated carboxylic acid and its sodium, potassium, lithium,
Metal salts such as zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, Α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; unsaturated dicarboxylic acids such as maleic acid and itaconic acid Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoglycone itaconate Glycol ester and the like unsaturated glycidyl group-containing monomers such as. Among these, vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester and the like are preferable.

The ethylene / polar monomer copolymer (C) may contain two or more units derived from the polar monomer.
The ethylene / polar monomer copolymer (C) has a unit derived from ethylene of 99.5 to
Units derived from polar monomers in a proportion of 0.5 mol%, preferably 99-1 mol%,
It is desirable to contain 0.5 to 99.5 mol%, preferably 1 to 99 mol%. In the present invention, the content of units derived from the polar monomer can be selected according to the use of the ethylene / polar monomer copolymer (C).

  In the ethylene / polar monomer copolymer (C), in addition to ethylene and the above polar monomer, one or more other monomers shown below are copolymerized within a range not impairing the object physical properties of the present invention. It may be.

Olefins other than ethylene, such as propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1 -Pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1
Α-olefins having 3 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclopentene, cycloheptene, norbornene, 5 -Number of carbon atoms such as methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 3-20 cyclic olefins and the like.

Examples of other monomers that may be copolymerized include styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, substituted vinylnaphthalenes, allylnaphthalenes, substituted allylnaphthalenes, and the like. Aromatic vinyl compounds; alicyclic vinyl compounds such as vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, allylnorbornane; allyltrimethylsilane, allyltriethylsilane Silane unsaturated compounds such as 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-decene; butadiene, 1,4-hexene Sadiene, 7-methyl-1,6-octadiene, 1,8-
Examples include conjugated or non-conjugated dienes such as nonadiene, 1,9-decadiene, norbornadiene, dicyclopentadiene, and the like.

  Specific preferred copolymers for the ethylene / polar monomer copolymer (C) include ethylene / acrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, Isopropyl acrylate copolymer, ethylene / n-butyl acrylate copolymer, ethylene / isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid Methyl copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / n-butyl methacrylate copolymer, ethylene isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer Polymer, ethylene-vinyl acetate copolymer, Len / vinyl propionate copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methacrylic acid Examples include acid glycidyl copolymers.

The ethylene / polar monomer copolymer (C) can be produced by a conventionally known method using ethylene and a polar monomer and, if necessary, other monomers.
As the ethylene / polar monomer copolymer (C), those having a refractive index in the range of 1.470 to 1.490 are preferably used. When the ethylene / polar monomer copolymer (C) having a refractive index within the above range is used, a polymer composition is obtained in which a cross-linked molded article having better transparency is obtained.

The refractive index is Abbe refractometer 2T type (Atago Co., Ltd.) according to ASTM D542.
And a sodium wire (λ ₀ = 589.3 nm).
The ethylene / polar monomer copolymer (C) is 1 to 150 parts by weight, preferably 3 to 100 parts by weight, more preferably 4 to 50 parts by weight, and still more preferably 100 parts by weight of the organic polymer (A). Is used in a proportion of 5 to 30 parts by weight. When the ethylene / polar monomer copolymer (C) is used within the above range, the resulting crosslinked molded article is particularly preferable because of excellent transparency.

Catalyst (D)
The catalyst (D) used as an optional component in the present invention is an addition reaction catalyst, and is an addition reaction between the alkenyl group of the organic polymer (A) and the SiH group of the SiH group-containing compound (B) (alkene hydrosilylation). The chemical reaction). Specifically, for example, an addition reaction catalyst composed of a platinum group element such as a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst (a group 8 metal catalyst such as a group 8 metal, a group 8 metal complex, or a group 8 metal compound in the periodic table) Among them, platinum-based catalysts are preferable.

The platinum-based catalyst may be a known one that is usually used for addition-curing type curing, such as a finely powdered metal platinum catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823, No. 218, chloroplatinic acid catalyst, U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662 complex of platinum and hydrocarbon, U.S. Pat. Complex of chloroplatinic acid and olefin described in U.S. Pat. No. 3,516,946, platinum and vinyl siloxane described in U.S. Pat. No. 3,775,452 and U.S. Pat. No. 3,814,780. And complex compounds. More specifically, platinum alone (platinum black), chloroplatinic acid, platinum-vinylsiloxane complex, platinum-olefin complex, platinum-alcohol complex, or a material such as alumina or silica that carries platinum. Can be mentioned.

  The palladium-based catalyst is composed of palladium, a palladium compound, palladium chloride acid, and the like, and the rhodium-based catalyst is composed of rhodium, rhodium compound, rhodium chloride acid, and the like.

Examples of the catalyst (D) other than the above include Lewis acid and cobalt carbonyl.
In the present invention, a platinum-vinylsiloxane complex is preferably used as the catalyst (D), and platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane is particularly preferable. Used.

The catalyst (D) is 0.1 to 1,000 ppm by weight, usually 0.1 to 500 ppm by weight, preferably 1 to 200 ppm by weight, more preferably, in terms of metal atoms, relative to the organic polymer (A). Is used in a proportion of 1 to 100 ppm by weight, particularly preferably 5 to 50 ppm by weight.

  When the catalyst (D) is used in a proportion within the above range, a polymer composition capable of forming a crosslinked molded article having a moderate crosslinking density, excellent strength properties and elongation properties, and excellent transparency and weather resistance can be obtained. .

  In the present invention, an uncrosslinked molded product of the polymer composition not containing the catalyst (D) can be irradiated with light, γ-rays, electron beams, etc. to obtain a crosslinked molded product. Can be continuously vulcanized.

Reaction inhibitor (E)
Examples of the reaction inhibitor (E) used as an optional component together with the catalyst (D) in the present invention include benzotriazole, ethynyl group-containing alcohols (eg, ethynylcyclohexanol), acrylonitrile, amide compounds (eg, N, N-diallylacetamide, N, N-diallylbenzamide, N, N, N ′, N′-tetraallyl-o-phthalic acid diamide, N, N, N ′,
N′-tetraallyl-m-phthalic acid diamide, N, N, N ′, N′-tetraallyl-p-phthalic acid diamide, etc.), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds , Organic peroxides such as tetramethyltetravinylcyclotetrasiloxane and hydroperoxide.

  The reaction inhibitor (E) is 0 to 20 parts by weight, usually 0.0001 to 15 parts by weight, preferably 0.0001 to 10 parts by weight, more preferably 0 to 100 parts by weight of the organic polymer (A). 0.0001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, and particularly preferably 0.1 to 0.5 part by weight.

  When the reaction inhibitor (E) is used in a proportion of 20 parts by weight or less, a polymer composition having a high crosslinking speed and excellent productivity and transparency of the crosslinked molded product can be obtained. If the reaction inhibitor (E) is used in a proportion exceeding 20 parts by weight, it is not preferable because it is disadvantageous in terms of cost.

Silica (F)
Silica (F) used as an optional component in the present invention refers to silicon oxide and may or may not contain crystal water and / or adsorbed water. Silica (F) is divided into silicic anhydride by a dry method, hydrous silicic acid by a wet method, and synthetic silicate. In the “Filler Handbook” issued by the Japan Rubber Association, the method for producing silica is described as follows.
(1) Method for Producing Silicic Anhydride (i) Method by Decomposing Silicon Halide (ii) Method for Obtaining Silicic Acid by Heating and Reducing Silica Sand (2) Method for Producing Hydrous Silicic Acid It is produced by the reaction of sodium acid and sulfuric acid.
(3) Production method of synthetic silicate Synthesized by reaction of sodium silicate and calcium salt.

Among these silicas, dry silica is preferable from the viewpoint of transparency because a continuous cross-linked molded product is difficult to fire, and a primary particle diameter of 20 nm or less is more preferable. The specific surface area of silica (F) is preferably 100 to 500 m ² / g.

  These silicas may be surface-treated with a reactive silane such as mercaptosilane, aminosilane, hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane.

  Silica (F) is used in a proportion of 1 to 100 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the organic polymer (A). Use of silica (F) within the above range is preferable in that a polymer composition excellent in transparency and extrudability can be obtained.

Other Components Although the crosslinkable polymer composition according to the present invention can be used as it is uncrosslinked, it can exhibit its characteristics most when used as a crosslinked product.

  In the crosslinkable polymer composition according to the present invention, a conventionally known inorganic filler, softening agent, anti-aging agent, processing aid, crosslinking aid, colorant, depending on the intended use of the crosslinked product, etc. Additives such as a dispersant and a flame retardant can be blended within a range that does not impair the object of the present invention.

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.
The kind and blending amount of these inorganic fillers can be appropriately selected depending on the application.

As the softener, a softener usually used for rubber can be used.
Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly;
Coal tar softeners such as coal tar and coal tar pitch;
Fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, coconut oil;
Tall oil;
sub;
Waxes such as beeswax, carnauba wax, lanolin;
Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate;
Examples thereof include synthetic polymer materials such as petroleum resins, atactic polypropylene, and coumarone indene resins. Of these, petroleum softeners are preferably used, and process oil is particularly preferably used.

The blending amount of these softeners is appropriately selected depending on the use of the crosslinked product.
Examples of the anti-aging agent include amine-based, hindered phenol-based, and sulfur-based anti-aging agents, and these anti-aging agents are used within the range not impairing the object of the present invention as described above. .

Examples of amine-based antioxidants include diphenylamines and phenylenediamines.
Specific examples of diphenylamines include p- (p-toluenesulfonylamide) -diphenylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, 4,4′-.
Dioctyl diphenylamine, high temperature reaction product of diphenylamine and acetone; low temperature reaction product of diphenylamine and acetone; low temperature reaction product of diphenylamine, aniline and acetone; reaction product of diphenylamine and diisobutylene; octylated diphenylamine, dioctyl Diphenylamine, p, p'-dioctyl diphenylamine, alkylated diphenylamine and the like.

Specific examples of phenylenediamines include N, N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, and N, N′-di-2.
-Naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N' -Bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine,
N, N′-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine And p-phenylenediamines such as phenyloctyl-p-phenylenediamine.

Among these, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine and N, N′-di-2-naphthyl-p-phenylenediamine are particularly preferable.
These compounds can be used alone or in combination of two or more.

Specific examples of the hindered phenol anti-aging agent include (1) 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
(2) 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol),
(3) 2,2-thiobis (4-methyl-6-tert-butylphenol),
(4) 7-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate,
(5) Tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane,
(6) Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
(7) Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate],
(8) 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
(9) 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine,
(10) Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate,
(11) 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate],
(12) N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy) -hydrocinnamide,
(13) 2,4-bis [(octylthio) methyl] -o-cresol,
(14) 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate-diethyl ester,
(15) Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane,
(16) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid ester,
(17) 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4-8,10- And tetraoxaspiro [5.5] undecane. Among these, phenol compounds (5) and (17) are particularly preferable.

As the sulfur-based anti-aging agent, a sulfur-based anti-aging agent usually used for rubber is used.
Specifically, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylimidazole, etc. Inhibitor;
Aliphatic thioether aging such as dimyristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate) An inhibitor etc. can be mentioned. Among these, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, pentaerythritol-tetrakis- (β-lauryl-thiopropio) Preferred).

  As said processing aid, the compound used for processing of a normal rubber can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; ricinoleic acid, stearic acid, palmitic acid and lauric acid And higher fatty acid esters.

  Such a processing aid is usually used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the organic polymer (A). It is desirable to determine the optimal amount.

In addition, other known rubbers can be blended into the crosslinkable polymer composition according to the present invention as long as the object of the present invention is not impaired.
Examples of such other rubbers include isoprene-based rubbers such as natural rubber (NR) and isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber. Mention may be made of conjugated diene rubbers such as (CR).

  Furthermore, a conventionally known ethylene / α-olefin copolymer can be used, for example, ethylene / propylene random copolymer (EPR), ethylene / α-olefin / polyene copolymer other than the organic polymer (A). (Eg, EPDM) can be used.

Preparation of Polymer Composition and Crosslinked Molded Body The crosslinkable polymer composition according to the present invention comprises an organic polymer (A), a SiH group-containing compound (B), an ethylene / polar monomer copolymer (C) and It can be prepared by mixing a compounding agent such as a catalyst (D) used as necessary by a conventionally known method. The cross-linked product according to the present invention can be produced by forming a cross-linkable polymer composition into an intended shape and then performing cross-linking.

The crosslinkable polymer composition according to the present invention is prepared, for example, by the following method.
That is, the crosslinkable polymer composition according to the present invention can be filled with an organic polymer (A) and optionally filled with an internal mixer (closed mixer) such as a Banbury mixer, a kneader, or an intermix. An additive such as an agent and a softening agent is preferably kneaded at a temperature of 80 to 170 ° C. for 3 to 10 minutes. Next, the kneaded product is mixed with a SiH group-containing compound (B), an ethylene / polar monomer copolymer (C ), If necessary, a catalyst (D) and a reaction inhibitor (E) are additionally mixed, and using a roll such as an open roll or a kneader, preferably kneaded at a roll temperature of 80 ° C. or lower for 1 to 30 minutes. Then, it can be prepared by dispensing.

  In the present invention, the organic polymer (A), the ethylene / polar monomer copolymer (C) and the inorganic filler can be kneaded at a high temperature, but the SiH group-containing compound (B) and the catalyst (D ) May be cross-linked (scorched) when kneaded at a high temperature at the same time, so when adding SiH group-containing compound (B) and catalyst (D) simultaneously, knead at 80 ° C. or lower. Is preferred. When one component is added among the SiH group-containing compound (B) and the catalyst (D), they can be kneaded even at a high temperature exceeding 80 ° C. In some cases, it is preferable to use cooling water against heat generated by kneading.

  When the kneading temperature in the internal mixer is low, together with the organic polymer (A), SiH group-containing compound (B), ethylene / polar monomer copolymer (C), inorganic filler, softener, etc. An antioxidant, a colorant, a dispersant, a flame retardant, and the like may be kneaded at the same time.

  The crosslinkable polymer composition according to the present invention prepared as described above has an intended shape by various molding methods using an extruder, a calender roll, a press, an injection molding machine, a transfer molding machine, and the like. The components can be introduced into the vulcanizing tank at the same time as the molding or can be crosslinked. A crosslinked product is obtained by heating at a temperature of 120 to 270 ° C. for 1 to 30 minutes or by irradiating with light, γ-rays or electron beams. In this crosslinking step, a mold may be used, or the crosslinking may be performed without using a mold. When a mold is not used, the molding and crosslinking processes are usually carried out continuously. As a heating method in the vulcanization tank, a heating tank such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave), steam or the like can be used.

  In the case of so-called non-dynamic crosslinking in which crosslinking is carried out after forming into an intended shape, it is particularly beneficial that crosslinking is possible in the presence of oxygen, in particular, crosslinking with hot air or the like. This is because if the crosslinking can be performed in the presence of oxygen, the crosslinking tank is sealed and it is not necessary to exclude oxygen, and the apparatus can be simplified and the process can be shortened. Such advantages are particularly remarkable when producing an extruded cross-linked molded body.

  In the case of using an organic polymer (A) having a low molecular weight and an ethylene / polar monomer copolymer (C), the organic polymer (A) and the copolymer (C) are in a liquid state. In a state, the SiH group-containing compound (B) can be mixed, and if necessary, the catalyst (D) and the reaction inhibitor (E) can be mixed, poured into a mold having an intended shape, and crosslinked at room temperature.

The crosslinked molded product obtained by crosslinking the crosslinkable polymer composition according to the present invention is excellent in transparency and weather resistance.
Uses of cross-linked molded products Cross-linked molded products according to the present invention include automobile weather strips, hoses (automobile hoses, water supply hoses, gas hoses), anti-vibration rubbers (anti-vibration rubbers for automobiles, anti-vibration rubbers for railways), Anti-vibration rubber for industrial machinery, seismic isolation rubber for construction), belts (power transmission belts, conveyor belts), sealing materials (cups and sealing materials for automobiles, sealing materials for industrial machinery), covered electric wires, electric wire joints, electrical insulation parts It can be suitably used for semiconductive rubber parts, rolls for OA equipment, industrial rolls, household rubber products, and the like.

  Furthermore, the crosslinked molded product according to the present invention can be suitably used for automobile interior materials, hard disk covers, electromagnetic wave shields, transparent hoses, wristwatch bands, semiconductor sealing materials, solar cell sealing materials, and the like.

  Examples of the automotive weather strip include a door weather strip, a trunk weather strip, a luggage weather strip, a roof side rail weather strip, a sliding door weather strip, a ventilator weather strip, a sliding loop panel weather strip, a front window weather strip, and a rear window weather. Strips, quarter window weather strips, lock pillar weather strips, door glass outer weather strips, door glass inner weather strips, dam windshields, glass run channels, door mirror brackets, seal headlamps, seal cowl tops.

Examples of the automobile hose include a brake hose, a radiator hose, a heater hose, and an air cleaner hose.
Examples of the anti-vibration rubber for automobile include, for example, engine mount, liquid seal engine mount, damper pulley, chain damper, carburetor mount, torsional damper, strut mount, rubber bush, bumper rubber, helper rubber, spring seat, shock absorber, air spring. , Body mount, bumper guard, muffler support, rubber coupling, center bearing support, clutch rubber, differential mount, suspension bush, sliding bush, cushion strut bar, stopper, handle damper, radiator supporter, muffler hanger, etc.

Examples of the anti-vibration rubber for railroad include slab mats, ballast mats, track mats and the like.
Examples of the industrial machine vibration-proof rubber include an expansion joint, a flexible joint, a bush, and a mount.

Examples of the transmission belt include a V belt, a flat belt, and a toothed belt.
Examples of the transport belt include a light transport belt, a cylindrical belt, a rough top belt, a transport belt with a flange, a transport belt with a U-shaped guide, and a transport belt with a V guide.

  Examples of the automobile cup / seal material include a master cylinder piston cup, a wheel cylinder piston cup, a constant velocity joint boot, a pin boot, a dust cover, a piston seal, a packing, an O-ring, and a diaphragm.

Examples of the industrial machine sealing material include capacitor packing, O-ring, packing and the like.
Examples of the automobile weather strip sponge include a door weather strip sponge, a bonnet weather strip sponge, a trunk room weather strip sponge, a sunroof weather strip sponge, a ventilator weather strip sponge, and a corner sponge.

Examples of the building seal sponge include gaskets, air tights, joint materials, door-to-door seal sponges, and the like.
Examples of the OA equipment roll include a charging roll, a transfer roll, a developing roll, and a paper feed roll.

Examples of the industrial roll include an iron-making roll, a paper-making roll, and a printing electric wire roll.
Examples of household rubber products include rain gear, rubber bands, shoes, rubber gloves, latex products,
A golf ball etc. are mentioned.

  The cross-linked molded product according to the present invention includes a cable joint, a semiconductor sealing material, an insulating sheet, an industrial hose, a floor material, a tile, a protective cover, a shoe cushion material, a pump tube, an electric decoration tube, a transparent building material gasket, It is particularly preferably used for packaging films, agricultural films, wristbands, flip flops, slippers, tapes, sports equipment, artificial turf mats and the like.

Moreover, the crosslinkable polymer composition according to the present invention can be crosslinked at room temperature, and is suitably used for reaction injection molding (RIM). Furthermore, it can be used in the production of thermoplastic elastomers and can also be used to modify engineering plastics.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

The composition, iodine value, intrinsic viscosity [η], and branching index of the copolymers used in Examples and Comparative Examples were measured by the following methods.
(1) Composition of copolymer The composition of the copolymer was measured by ¹³ C-NMR method.
(2) Iodine value of copolymer The iodine value of the copolymer was determined by a titration method.
(3) Intrinsic viscosity [η]
The intrinsic viscosity [η] of the copolymer was measured in decalin at 135 ° C.
(4) Branching index The frequency dispersion of the complex viscosity η ^* was measured using a dynamic viscoelasticity tester for EPR (four samples having different molecular weights) having no long chain branching.

The complex viscosity η ^* at 0.01 rad / sec and 8 rad / sec is obtained, and the complex viscosity η _1L ^* (0.
01 rad / sec) is plotted on the vertical axis, and the complex viscosity η _2L ^* (8 rad / sec) is plotted on the horizontal axis to create a reference line, and η _2L ^* = 1 × 10 ³ / Pa on the extension of the line • η _1L0 ^{* at s} was measured.

Next, similarly for the target sample, the complex viscosity η ^* at 0.01 rad / sec and 8 rad / sec is obtained, and the complex viscosity η _1B ^* (0.01 rad / sec) is plotted on the vertical axis. The rate η _2B ^* (8 rad / sec) is plotted on the horizontal axis. This plot has a larger value than the reference line, and the longer the long chain branch, the larger the distance from the reference line.

Next, the reference line was translated so as to pass over the plot, and the intersection point η _1B0 ^* with the complex viscosity η ₂ ^* = 1 × 10 ³ / Pa · s was measured.
The branching index was calculated by applying the values of η _1L0 ^* and η _1B0 ^* measured as described above to the following equation.

Branch index = ( _{logη 1L0} ^* −logη _1B0 ^* ) × 10
The measurement conditions are as follows.
Reference sample: 4 types of EPR
Tuffmer P-0280, P-0480, P-0680, P-0880 (trade name, manufactured by Mitsui Chemicals, Inc.)
-Dynamic viscoelasticity tester (RDS): Rheometrics company-Sample: Used by punching a 2 mm sheet into a 25 mm diameter circle.
・ Temperature: 190 ℃
-Distortion rate: 1%-Frequency dependence: 0.001-500 rad / sec
Moreover, the component used by the Example and the comparative example is as follows.

[EPT (1)]
PX-055 manufactured by Mitsui Chemicals, Inc.
Mooney viscosity ML _{1 + 4} (100 ° C.) = 8, ethylene content = 59 wt%, diene content = 4
. 5% by weight, [η] = 1.0 dl / g, iodine value = 9.0, branching index = 18.4
[EPT (2)]
Mitsui EPT # 4010 (trade name) manufactured by Mitsui Chemicals, Inc.
Mooney viscosity ML _{1 + 4} (100 ° C.) = 8, ethylene content = 59 wt%, diene content = 8
. 0% by weight, [η] = 1.0 dl / g
[Ethylene / vinyl acetate copolymer]
EVA # 150 (trade name) manufactured by Mitsui DuPont Polychemical Co., Ltd.
Vinyl acetate content = 33 wt%, density = 960 kg / m ³ , MFR = 30 g / 10 min, melting point = 61 ° C., refractive index = 1.482
[SiH group-containing compound]
Organohydrodiene polysiloxane (trade name) X-93-1346 manufactured by Shin-Etsu Chemical Co., Ltd.
(Structural formula)
_{(CH 3) 3 SiO - [} - SiH (CH 3) -O-] 6 - [- Si (CH 3) 2 -O-] 1 - [- Si (Ph) 2 -O-] 1 -Si (CH ₃ ) ₃ … (IV)
(However, in the compound represented by the above formula (IV), [—SiH (CH ₃ ) —O—], [—Si (CH ₃ ) ₂ O—], [—Si ( (Ph) ₂ —O—] is bonded at random, and Ph represents a phenyl group.)

  First, 100 parts by weight of EPT (1) was masticated for 1 minute, and further 15 parts by weight of an ethylene / vinyl acetate copolymer (trade name: EVA # 150, manufactured by Mitsui DuPont Polychemical Co., Ltd.) and a crosslinking agent (SiH (Group-containing compound) 4 parts by weight were mixed, kneaded for 2 minutes, and discharged at about 140 ° C. to obtain a blend. This kneading was performed at a filling rate of 70%.

100 parts by weight of the above composition was wound around a 6-inch roll (front roll surface temperature 60 ° C., rear roll surface temperature 60 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and an inhibitor (1- Ethynyl-1-cyclohexanol 0.3 parts by weight, catalyst (platinum-1,
3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 0.1
% Concentration IPA solution) 0.2 parts by weight was added and kneaded for 10 minutes, and then dispensed into a sheet and pressed at 180 ° C. for 10 minutes to prepare a vulcanized sheet having a thickness of 2 mm.

[Continuous crosslinkability]
The unvulcanized rubber sheet was allowed to stand in a HAV (hot air vulcanization tank) at 200 ° C. for 5 minutes to produce a crosslinked sheet without pressure.

The obtained crosslinked sheet was subjected to a scratch resistance test according to the following method.
[Scratch resistance test]
The surface of the crosslinked sheet immediately after taking out from the HAV (hot air vulcanizing tank) was scratched with a pencil of HB, the scratched state was observed with the naked eye, and scratch resistance was evaluated in two stages. ○ is excellent in continuous crosslinkability.

<Evaluation of scratch resistance>
○: The surface is not scratched at all ×: The surface is scratched [Haze value (cloudiness value) measurement conditions]
Measurement was performed according to JIS K7105. The thickness of the test piece was 2 mm.

[Hue]
It measured based on JISK-7105. The thickness of the test piece was 2 mm.
[Weatherability]
The test piece whose haze and hue were measured was put into a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) (irradiation time / rainfall time = 112/18 minutes) black panel = 63 ° C. and treated for 1000 hours to obtain a haze value and hue. Was measured.

In Example 1, it carried out like Example 1 except having used the usage-amount of the ethylene-vinyl acetate copolymer 30 weight part.
[Comparative Example 1]
In Example 1, EPT (2) was used instead of EPT (1), and 2.7 parts by weight of dicumyl peroxide (trade name: Kayakumiru DCP-40C, manufactured by Kayaku Akzo) was used as a crosslinking agent. Was carried out in the same manner as in Example 1.
[Comparative Example 2]
In Example 1, EPT (2) was used instead of EPT (1), 1.0 part of sulfur as a crosslinking agent, 0.5 part of N-cyclohexyl-2-benzothiazolesulfenamide (CBS), dibutyldithiocarbamic acid Other than using 0.7 parts of zinc (ZnDBC), 0.7 parts of tetramethylthiuram disulfide (TMTD), 0.7 parts of dipentamethylene thiuram tetrasulfide (DPTT), 0.5 parts of tellurium diethyldithiocarbamate (TeEDC) Was the same as in Example 1.

  The above results are shown in Table 1 below.

Claims (8)

The non-conjugated polyene is at least one ethylene / α-olefin / non-conjugated polyene random copolymer represented by the following general formula (I) or (II):

Wherein n is an integer from 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ),

(In the formula, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
(I) The molar ratio (ethylene unit / α-olefin unit) of the ethylene unit and the α-olefin unit having 3 to 20 carbon atoms is in the range of 60/40 to 85/15,
(Ii) the iodine value is in the range of 0.5-30 g / 100 g;
(Iii) The intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is in the range of 0.3 to 3.0 dl / g,
(Iv) an organic polymer (A) having a branching index of 5 or more determined by a dynamic viscoelasticity meter, a SiH group-containing compound (B) having at least two SiH groups in one molecule, and ethylene / acetic acid A vinyl copolymer (C),
It contains 0.1 to 100 parts by weight of the SiH group-containing compound (B) and 1 to 150 parts by weight of the ethylene / vinyl acetate copolymer (C) with respect to 100 parts by weight of the organic polymer (A). A crosslinkable polymer composition.   The crosslinkable polymer composition according to claim 1, wherein the ethylene / vinyl acetate copolymer (C) has a refractive index in the range of 1.470 to 1.490. The polymer composition further comprises (D) an addition reaction catalyst in an amount of 0.1 to 1,000 ppm by weight with respect to the organic polymer (A) in terms of metal atoms. Item 3. The crosslinkable polymer composition according to Item 1 or 2. The crosslinkable polymer composition according to claim 3, wherein the addition reaction catalyst (D) is a platinum-vinylsiloxane complex. The said polymer composition contains 0.0001-20 weight part of crosslinking reaction inhibitors (E) with respect to 100 weight part of organic polymers (A) further. 5. The crosslinkable polymer composition according to any one of 4 above.   The said polymer composition contains 1-100 weight part of silica (F) with respect to 100 weight part of organic polymers (A) further, The any one of Claims 1-5 characterized by the above-mentioned. A crosslinkable polymer composition as described.   A molded product obtained by crosslinking the crosslinkable polymer composition according to claim 1.   The molded body according to claim 7, wherein the molded body is an electrical / insulating part or an industrial part.