JP2881751B2 - Plating composition and plating - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition for plating and a plated product, and more particularly, to heat resistance, chemical resistance, boiling water resistance,
The present invention relates to a resin composition capable of forming a plated article having excellent heat aging resistance and impact resistance, and a metal plated article formed from the resin composition.

Technical background of the invention In order to give metallic luster to resin molded products for decoration,
Alternatively, a metal plating may be applied to the surface to shield electromagnetic waves or the like. Known methods for plating a metal on the surface of a resin molded body include a chemical plating method, a conductive paint method, a vapor deposition method, and a gas phase method.

By the way, the present applicant has already applied for a cyclic olefin-based resin as a resin having excellent heat resistance, heat aging resistance, chemical resistance and the like (for example, Japanese Patent Application Laid-Open No. 60-26024).
And JP-A-60-168708 and JP-A-61-115912).

By providing a metal plating layer on the surface of a molded article made of such a cyclic olefin-based resin, heat resistance, heat aging resistance, chemical resistance, etc. are excellent, the surface has a metallic luster, and further, electromagnetic wave shielding properties A molded article having excellent properties such as the above can be obtained.

However, when metal plating is actually performed on such a cyclic olefin polymer, a molded article formed from the cyclic olefin resin may not be easily formed.

Object of the Invention It is an object of the present invention to provide a resin composition which can be plated using a cyclic olefin polymer as a resin component.

Another object of the present invention is to provide a molded article formed from a resin containing the above resin composition, wherein a metal is provided with a plating layer on the surface thereof, so that heat resistance, heat aging resistance, chemical resistance, boiling water resistance and impact resistance are obtained. An object of the present invention is to provide a plated material having excellent properties.

SUMMARY OF THE INVENTION The plating composition according to the present invention comprises a cyclic olefin ring-opening polymer represented by the following formula [I], a ring-opening copolymer, a hydrogenated product of the polymer and the copolymer, and A cyclic olefin resin (component (A)) selected from the group consisting of an addition polymer of a cyclic olefin represented by the formula [I] and ethylene, and 100 parts by weight of the cyclic olefin resin,
5-100 parts by weight of a soft polymer (component (B)), and the soft polymer as the component (B) comprises (i) an ethylene component unit and an α-olefin component unit other than ethylene. And a cyclic olefin component unit represented by the following formula [I], and has an intrinsic viscosity [η] of 0.01 to 10 dl / g and a glass transition temperature Tg of 0 measured in decalin at 135 ° C.
(Ii) an amorphous or low-crystalline α-olefin copolymer having a glass transition temperature Tg of 0 ° C or lower formed from at least two kinds of α-olefins. (Iii) an α-olefin / diene-based copolymer having a glass transition temperature Tg of 0 ° C. or lower formed from at least two kinds of α-olefins and at least one kind of non-conjugated diene; (iv) glass transition An aromatic vinyl hydrocarbon / conjugated diene random or block copolymer having a temperature Tg of 0 ° C. or less, or a hydride thereof; and (v) a soft polymer or copolymer comprising isobutylene or isobutylene and a conjugated diene. It is characterized by being at least one kind of resin selected from the group consisting of:

In the above formula [I], n is 0 or a positive integer, and R ^{1 to} R ¹² each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group; ⁹ to R ^12, which may be may be bonded to form a monocyclic or polycyclic group each other, and the monocyclic or polycyclic group having a double bond and, R ⁹ And R ¹⁰ or R ¹¹ and R ¹² may form an alkylidene group.

Furthermore, the plated product according to the present invention is characterized in that a metal molded layer is formed on at least a part of the surface of the resin molded body formed from the plating composition as described above.

The present invention provides a cyclic olefin polymer excellent in heat resistance, heat aging resistance, chemical resistance and boiling water resistance, and by blending a specific soft polymer, the adhesion between the resin and the plating metal is extremely high. This is based on the knowledge that it will be good. By using the composition provided by the present invention, it is possible to provide a plated material that can sufficiently cope with recent diversification of applications.

The metal layer as a plating layer of the present invention is a chemical plating method,
It is formed on the surface of the plating composition by a conductive paint method, a vapor deposition method, a vapor phase method, or the like.

However, such a metal layer can form a good plating layer on the surface of the formed molded body when a cyclic olefin-based resin is used alone, for example, as shown in a comparative example described later. Can not.

Therefore, the present inventor has found that by mixing a specific amount of a specific soft polymer as the component [B] with the cyclic olefin-based resin as the component [A], the adhesion to a metal is improved. Therefore, the composition for plating of the present invention,
The cyclic olefin resin as the component (A) includes (i) to
The component (B) of (v) is blended. This [B] component is
[A] By blending in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the component, the composition for plating has a remarkably enhanced adhesion to the metal layer, and a uniform metal layer is formed on the surface thereof.
The impact strength is also improved.

The molded body formed from the plating composition may have been subjected to physical and chemical treatments such as mechanical treatment, chemical corrosion treatment, sensitization and activation treatment of the surface.

The component [A] of the present invention enhances the heat resistance, heat aging resistance, chemical resistance, and boiling water resistance of the composition for plating, so that the aforementioned resin is subjected to mechanical treatment, chemical corrosion treatment, sensitization, and activation. In the treatment and the like, the composition can be easily treated without fear of causing excessive corrosion or the like. Further, the metal of the plating layer is not limited to copper, silver, nickel, or the like which can be an industrial material, but may be gold or another decorative material.

Next, the plating composition and the plated product of the present invention will be specifically described.

[Cyclic Olefin Component] The plating composition according to the present invention is formed from a cyclic olefin resin and a soft polymer.

The cyclic olefin-based resin includes a polymer, a copolymer and a hydrogenated product thereof obtained by ring-opening polymerization of the cyclic olefin represented by the formula [I], and a cyclic olefin represented by the following formula [I], ethylene and Is selected from the resins consisting of copolymers formed by addition polymerization.

However, in the above formula [I], n is 0 or a positive integer, and R ^{1 to} R ¹² are each independently a hydrogen atom,
Represents a group or an atom selected from the group consisting of a halogen atom and a hydrocarbon group. Further, R ^{9 to} R ¹² may form a monocyclic or polycyclic group bonded to each other, and this ring may have a crosslinked structure. Further, this monocyclic or polycyclic group may have a double bond. Further, a group in which these rings are combined may be used.

That is, R ^{9 to} R ¹² may form a polycyclic or monocyclic group as described below, for example.

In addition, in the above formula, the carbon atom to which 1 and 2 are given represents a carbon atom of the alicyclic structure to which the groups represented by R ^{9 to} R ¹² are bonded in the formula [I]. Further, these groups may have a substituent such as a methyl group.

Further, R ⁹ and R ¹¹ , or R ¹⁰ and R ¹² may form an alkylidene group. Further, an ester group or the like may be included in R ^{9 to} R ¹² .

Among such cyclic olefins, preferred examples include, for example, cyclic olefins represented by the following formula [II].

However, in the above formula [II], n is 0 or 1, m is 0 or a positive integer, and R ^{1 to} R ¹⁸ each independently represent a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Represents an atom or a group selected from

Further, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond.

Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group.

The olefin polymer having an alicyclic structure is, for example, a ring-opened polymer obtained by ring-opening polymerization of the formula [I], or preferably, the formula [II] alone or in the presence of the compound as shown in the following formula, or It may be a ring-opening copolymer. Further, in the present invention, a hydrogenated product obtained by hydrogenating at least a part of the double bond present in the ring-opening polymer or the ring-opening copolymer as described above can also be used. .

The cyclic olefin represented by the above formula [I] or, preferably, the formula [II] can be easily produced by condensing cyclopentadiene and the corresponding olefin or cyclic olefin by a Diels-Alder reaction. it can.

Specific examples of the cyclic olefin represented by the formula [I] used in the present invention include bicyclo [2,2,
1] hept-2-ene derivatives, tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives, hexacyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14] −
4-heptadencene derivatives, octacyclo [8,8,0,1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 1 ^13.16 ,
0 ^3.8, 0 ^12.17] -5-docosene derivatives, pentacyclo [6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14] -4-hexadecene derivative, heptacyclo-5-icosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4,3,0,1 ^2.5] -3-decene derivatives, tricyclo [4,3,0,1 ^2.5] -3-undecene derivatives, pentacyclo [6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13] 4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3-pentadecene derivatives, pentacyclo [7,8,0,1 ^3.6, 0 ^2.7, 1 ^10.17 , 0 ^11.16 , 1
^12.15] -4-eicosene derivatives, and Nonashikuro [9,10,1,1,4.7,0 ^3.8, 0 ^2.10, 0 ^12.21, 1
^13.20, 0 ^14.19, may be mentioned 1 ^15.18] -5-pentacosene derivatives.

 Specific examples of such compounds are shown below.

Bicyclo [2,2,1] hept-2-ene derivatives such as; Tetracyclo such [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives; Hexacyclo such as [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7 0 ^9.14]
-4-heptadecene derivatives; Octacyclo [8,8,0,1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 1 ^13.16 ,
0 ^3.8 , 0 ^12.17 ] -5-docosene derivative; Pentacyclo such as [6,6,1,1 ^3.6, 0 ^2.7 0 ^9.14] -4
Hexadecene derivatives; A heptacyclo-5-icosene derivative or a heptacyclo-5-heneicosene derivative; Tricyclo [4,3,0,1 ^2.5] -3-decene derivatives such as; Tricyclo [4,4,0,1 ^2.5] -3-undecene derivatives such as; Pentacyclo such as [6,5,1,1 ^3.6, 0 ^2.7 0 ^9.13] -4
Pentadecene derivatives; Diene compounds such as; Pentacyclo such [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3
Pentadecene derivatives; Heptacyclo such as [7,8,0,1 ^3.6, 0 ^2.7, 1 ^10.17, 0 ^11.16,
1 ^12.15 ] -4-Eicosene derivative; Nonacyclo [9,10,1,1 ^4.7 , 0 ^3.8 , 0 ^2.10 , 0 ^12.21 , 1
^13.20, 0 ^14.19, may be mentioned 1 ^15.18] -5-pentacosene derivatives.

And furthermore, Can be mentioned.

Specific examples of the polycyclic olefin represented by the formula [I] include the compounds described above or 1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 2
-Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Propyl-1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5, 8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2- Chloro-1,4,5,8-dimethano
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-
Dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-isobutyl-
Octahydronaphthalenes such as 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene can be exemplified.

[Cyclic olefin-based polymer: component [A]] The cyclic olefin-based polymer used in the plating composition of the present invention includes: (1) a ring-opened polymer of a cyclic olefin represented by the above formula [I] Or, a ring-opened copolymer or a hydrogenated product thereof and (2) a copolymer obtained by addition polymerization of the cyclic olefin represented by the above formula [I] and ethylene.

(1) Cyclic olefin ring-opening polymer and hydrogenated product thereof A cyclic olefin ring-opening polymer is obtained by subjecting a cyclic olefin represented by the above formula [I], preferably [II], to ring-opening polymerization by a method known per se. And homopolymerized or copolymerized. For example, 1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-Octahydronaphthalenes are copolymerized with each other or the above-mentioned norbornene (bicyclo [2.2.1] hept-2-ene) is copolymerized. May be used.

In the ring-opened polymer or ring-opened copolymer of a cyclic olefin as described above, for example, at least a part of the cyclic olefin represented by the formula [II] has a structure represented by the following formula [III]. It is thought that there is.

The ring-opened polymer can easily hydrogenate the remaining double bond by a method known per se, and the hydrogenated product has better thermal stability and better weather resistance.

In such a hydrogenated product, for example, at least a part of the cyclic olefin represented by the formula [II] is, for example, represented by the following formula [I
V].

In the formulas [III] and [IV], R ^{1 to} R ¹⁸ have the same meaning as in the formula [II].

When the ring-opening polymerization of the cyclic olefin is carried out, the ring-opening (co) polymer formed from the cyclic olefin represented by the above formula [I] or preferably by the above formula [II] is used in a range not to impair the physical properties. Can be subjected to ring-opening copolymerization. Examples of such cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 2,3,3a, 7a-tetrahydro- 4,7-methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7-methano-
1H-indene and the like can be mentioned.

(2) A copolymer obtained by addition polymerization of a cyclic olefin and ethylene (sometimes referred to as a cyclic olefin addition polymer).
The cyclic olefin component (molar ratio) is usually 10/90 to 90/10, preferably 50/50 to 75/25. The production of the ethylene copolymer is carried out by polymerizing ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. Such a polymerization method is already known and has been proposed in JP-A-60-168708 and the like.

In addition, in the cyclic olefin addition polymer, other than the cyclic olefin component and the ethylene component, other than the α-olefin component and / or the cyclic olefin represented by the formula [I] or [II], as long as the properties of the polymer are not impaired. A random copolymer obtained by addition polymerization of the above-mentioned cyclic olefin component may be used in the plating composition according to the present invention.

The α-olefin is linear or branched, for example, propylene, 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene,
Examples thereof include α-olefins having 3 to 20 carbon atoms, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among them, 3 to 15 carbon atoms, particularly 3 to
Ten α-olefins are preferred.

The other cyclic olefin component herein is a compound other than the cyclic olefins of the formulas [I] and [II], and includes all compounds recognized as unsaturated polycyclic hydrocarbon compounds. It is a concept.

More specifically, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-
Cyclohexene, styrene, α-methylstyrene, 2,3,
Examples include 3a, 7a-tetrahydro-4,7-methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene.

Further, as the cyclic olefin other than the cyclic olefin represented by the formula [I] or the formula [II], a compound having two or more double bonds in a molecule can be used in addition to the compounds exemplified above. Further, when such a compound is used, the double bond not used in the addition polymerization reaction may be left unsatisfactory, but the double bond may be used for the purpose of improving the weather resistance of the molded article. Hydrogenation can also be performed.

In the above cyclic olefin addition polymer, for example, at least a part of the cyclic olefin represented by the formula [I] forms a polymer by forming a structure represented by the following formula [V]. it is conceivable that.

However, in the above formula [V], m and n and
R ^{1 to} R ¹⁸ have the same meaning as those in the formula [I].

Such a cyclic olefin addition polymer has a chemically stable structure and is a polymer excellent in heat aging resistance.

The above-mentioned (1) cyclic olefin ring-opening polymer and its hydrogenated product and (2) cyclic olefin addition polymer have an intrinsic viscosity [η] of 0.03 measured in decalin at 135 ° C.
1-10 dl / g, especially 0.05-10 dl / g, and even 0.08-8
dl / g is preferred.

These cyclic olefin polymers are generally amorphous or low-crystalline, and are preferably amorphous. Generally, the degree of crystallinity by X-rays is 5% or less, most of them are 0%, and many have no melting point observed by a differential scanning calorimeter (DSC).

Another property of such a cyclic olefin polymer is that it has a high glass transition temperature Tg and a high softening temperature (TMA). The glass transition temperature Tg is usually measured in the range of 50 to 230 ° C, most often in the range of 70 to 210 ° C. Therefore, when used directly for molding materials, the softening temperature is usually measured within the range of 60 to 240 ° C, and most often within the range of 80 to 220 ° C.

The thermal decomposition temperature is in the range of 350 to 420 ° C, and most often in the range of 370 to 400 ° C.

As a mechanical property, the flexural modulus is usually 1 × 10 ^{4 to} 5 × 10 ⁴
in the range of kg / cm ^2, bending strength usually 300~1500kg / cm
^{It is in} the range of ² .

The density of this composition is usually 0.86 to 1.10 g / c.
m ² , most of which are in the range of 0.88 to 1.08 g / cm ² . The refractive index (measured by ASTM D542) is 1.47 to 1.58, and most of them are 1.
It is in the range of 48 to 1.56.

As electrical properties, the dielectric constant (1 KHZ) measured by ASTM D150 is 1.5 to 3.0, most is 1.9 to 2.6, and the dielectric loss tangent is 9 ×
It is in the range of 10 ^-4 to 8 × 10 ^-5 , often in the range of 3 × 10 ^{-4 to} 9 × 10 ^-5 .

[Soft polymer; component [B]] Adhesion with the metal plating layer is improved by blending this soft polymer. The soft polymer that can be used in the present invention includes (i) to (v) described below.
And rubber-like components selected from the group of

Soft polymer having a repeating unit derived from a cyclic olefin (i) The soft polymer having a repeating unit derived from a cyclic olefin is ethylene and the cyclic olefin shown in the description of the cyclic olefin polymer ( A copolymer represented by the formula [I], preferably a compound represented by the formula [II], and an α-olefin component. As the α-olefin, for example, propylene, 1-butene, 4-methyl-
Examples thereof include 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Of these, α-olefins having 3 to 20 carbon atoms are preferred. Also, cyclic olefins and / or cyclic dienes such as norbornene, ethylidene norbornene, dicyclopentadiene and the like can be used.

In preparing the flexible polymer (i) having a repeating unit derived from a cyclic olefin, ethylene is used in an amount of 40%.
To 98 mol%, preferably 50 to 90 mol%. The α-olefin is used in an amount ranging from 2 to 50 mol%, and the cyclic olefin is used in an amount ranging from 2 to 20 mol%, preferably from 2 to 15 mol%.

The soft polymer (i) has a glass transition temperature (Tg) of 0 ° C. or lower, preferably −10 ° C. or lower, and is different from the cyclic olefin polymer of the component [A]. Is 0.01 to 10 dl / g, preferably 0.8 to 7 dl / g. The flexible polymer (i) has a crystallinity of 0 to 10%, preferably 0 to 7 as measured by X-ray diffraction.
%, Particularly preferably in the range of 0 to 5%.

This soft polymer (i) is disclosed in JP-A-60-168708,
JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62 According to the method proposed by the present applicant in Japanese Patent Publication No. 252406 and the like, the production can be carried out by appropriately selecting conditions.

α-olefin-based copolymer (ii) The α-olefin-based copolymer (ii) used as the soft polymer is an amorphous or low-crystalline copolymer composed of at least two kinds of α-olefins. It is. Specific examples include an ethylene / α-olefin copolymer and a propyne / α-orene fin copolymer.

In preparing the ethylene / α-olefin copolymer, an α-olefin having 3 to 20 carbon atoms is usually used. Specifically, propylene, 1-butene, 4-
Methyl-1-butene, 1-hexene, 1-octene, 1
-Decene, etc., or a mixture thereof. Of these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

The molar ratio (ethylene / α-olefin) of the repeating unit derived from ethylene to the repeating unit derived from α-olefin in the ethylene / α-olefin copolymer varies depending on the type of α-olefin,
Generally 40/60 to 95/5. When the α-olefin is propylene, the molar ratio is preferably 40/60 to 90/10, and the α-olefin is α having 4 or more carbon atoms.
-When it is an olefin, it is preferably 50/50 to 95/5.

In preparing the propylene / α-olefin copolymer, usually an α-olefin having 4 to 20 carbon atoms is used. Specific examples include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and the like, or a mixture thereof. Of these, α-olefins having 4 to 10 carbon atoms are particularly preferred.

In the propylene / α-olefin copolymer as described above, a repeating unit derived from propylene and α
-The molar ratio with the repeating unit derived from olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50 to 95/5.

α-olefin / diene copolymer (iii) Examples of the α-olefin / diene copolymer (iii) used as the soft polymer include ethylene / α-olefin / diene copolymer rubber and propylene / α. -Olefin / diene copolymer rubber.

In preparing these copolymer rubbers, α-olefins having 3 to 20 carbon atoms are usually used, for example, propylene, 1-butene, 1-pentene and 4-methyl-1.
Examples include pentene, 1-hexene, 1-octene, 1-decene, and mixtures thereof. Of these, α-olefins having 3 to 10 carbon atoms are preferred. However, in the case of a propylene / α-olefin / diene copolymer, the α-olefin has 4 to 20 carbon atoms.

The diene components constituting these copolymer rubbers are 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene and 7- Chain non-conjugated dienes such as methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Isopropylidene-2-
Cyclic unconjugated dienes such as norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene, and 2,3-diisopropylidene-5-norbornene;
Examples include 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

In the ethylene / α-olefin / diene copolymer rubber, a repeating unit derived from ethylene and α-
The molar ratio to the repeating unit derived from olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is usually 40/60 to 90/10.

The content of the repeating unit derived from the diene component in these copolymer rubbers is usually 1 to 20 mol%, preferably 2 to 15 mol%.

Aromatic vinyl hydrocarbon / conjugated diene soft copolymer or hydride thereof (iv) The aromatic vinyl hydrocarbon / conjugated diene soft copolymer used as the soft polymer is an aromatic vinyl hydrocarbon. And a conjugated diene compound and a random copolymer, a block copolymer or a hydride thereof. Specific examples include styrene / butadiene block copolymer rubber, styrene / butadiene / styrene block copolymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber,
Examples include hydrogenated styrene / butadiene / styrene block copolymer, hydrogenated styrene / isoprene / styrene block copolymer rubber, and styrene / butadiene random copolymer rubber.

In these copolymer rubbers, the molar ratio of the repeating unit derived from an aromatic vinyl hydrocarbon to the repeating unit derived from a conjugated diene (aromatic vinyl hydrocarbon / conjugated diene) is usually 10/90 to 70/30. Further, the hydrogenated copolymer rubber is a copolymer rubber obtained by hydrogenating a part or all of the double bonds remaining in the above-mentioned copolymer rubber.

Soft polymer or copolymer (v) composed of isobutylene or isobutylene / conjugated diene As the isobutylene-based soft polymer or copolymer (v) used as the soft polymer, specifically, polyisobutylene rubber, polyisobutylene For example, isoprene rubber, polybutadiene rubber, or isobutylene / isoprene copolymer rubber is used.

The properties of the soft polymers (ii) to (v) are the same as the properties of the cyclic olefin-based soft polymer (i), and these soft polymers were measured in decalin at 135 ° C. The intrinsic viscosity [η] is usually in the range of 0.01 to 10 dl / g, preferably 0.08 to 7 dl / g, and the glass transition temperature (T
g) is usually 0 ° C. or lower, preferably −10 ° C. or lower, particularly preferably −20 ° C. or lower. The crystallinity measured by the X-ray diffraction method is 0 to 10%, preferably 0 to 7%.
%, Particularly preferably in the range from 0 to 5%.

Such a rubbery component ([B] component) is added to 100 parts by weight of the cyclic olefin addition polymer as the [A] component.
It is used in an amount ranging from 5 to 100 parts by weight, preferably from 5 to 80 parts by weight, particularly preferably from 10 to 50 parts by weight. Here, the rubbery component ([B] component) can be used alone or in combination of two or more. When two or more rubber-like components are used in combination, the content of the rubber-like components in the resin composition of the present invention is the total content of the rubber-like components.

By setting the content (total amount) of the soft polymer [B] component in the resin composition of the present invention in the range of 5 to 100 parts by weight, the surface of a molded article produced from this resin composition is excellent. Can be plated,
The molded article has good impact strength, rigidity and hardness, and the heat deformation temperature of the resin is also within a good range. That is, when the content of the soft polymer is significantly lower than 5 parts by weight, plating is difficult to be applied on the surface of the molded body, and the impact strength of the molded body tends to be reduced. On the other hand, when the amount of the soft polymer greatly exceeds 100 parts by weight, the heat deformation temperature of the resin composition tends to decrease, and the rigidity and hardness of the molded article tend to decrease.

Although the resin composition of the present invention is a composition containing a cyclic olefin polymer and a soft polymer as described above, the composition may have a crosslinked structure. That is,
A crosslinked structure may be formed by using an organic peroxide in the composition of the present invention comprising the component [A] of the cyclic olefin polymer and the component [B] of the soft polymer. By using a crosslinked polymer alloy (crosslinked polymer alloy) prepared in this manner, plating properties, impact resistance,
It is possible to obtain a composition capable of forming a molded article having a particularly excellent balance of properties such as heat deformation temperature.

Examples of the organic peroxide used in this case include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroiside, and 1,1-bis (t-
Peroxy ketals such as butyl peroxy) cyclohexane 2,2-bis (t-butyl peroxy) octane;
hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxy peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide; Dialkyl such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Diacyl peroxides such as peroxide, lauroyl peroxide and benzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxy benzoate, 2,5-
Peroxyesters such as dimethyl-2,5-di (benzoylperoxy) hexane and the like can be mentioned.

The organic peroxide component is usually 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the total amount of the cyclic olefin addition polymer and the soft polymer component. used.

In forming the crosslinked structure as described above, a compound having two or more radically polymerizable functional groups in a molecule may be blended. By abolishing the compound having two or more radically polymerizable functional groups in the molecule, the crosslinking efficiency is increased.

Examples of the compound having two or more radically polymerizable functional groups in the molecule used herein include divinylbenzene, vinyl acrylate, vinyl methacrylate and the like. These compounds are used in an amount of usually 1 part by weight or less, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total amount of the cyclic olefin addition polymer and the soft polymer.

[Other Additives] An inorganic filler can be added to the plating composition according to the present invention. The inorganic filler reacts with or dissolves in the etching solution in the etching step at the time of the plating treatment, so that the surface state of the molded body by the etching solution is more efficiently adjusted. Examples of the inorganic filler that can be used here include wollastonite, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. The blending amount of the filler component is the total amount of the component [A] and the component [B].
The amount is usually 100 parts by weight or less, preferably 5 to 50 parts by weight, per 100 parts by weight.

The plating composition according to the present invention further includes a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, an anti-fogging agent as long as the object of the present invention is not impaired.
Lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers and the like can be blended.

For example, examples of stabilizers incorporated as optional components include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and β- (3,5-di- t-butyl-4-hydroxyphenyl) propionic acid alkyl ester and 2,2'-oxamidobis [ethyl-3- (3,5-di-t-butyl-
Phenolic antioxidants such as 4-hydroxyphenyl) propionate; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 1,2-hydroxystearate; and glycerin monostearate, glycerin distearate, and pentaerythritol monostearate And fatty acid esters of polyhydric alcohols such as pentaerythritol distearate and pentaerythritol tristearate. These may be blended alone or in combination. When combined and used, for example, tetrakis [methylene-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate], a combination of methane, zinc stearate, and glycerin monostearate.

Further, as an organic or inorganic filler, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide,
Pumice powder, pumice balloon, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite , Graphite, aluminum powder, molybdenum sulfide,
Examples include Teflon powder, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber and the like.

As a method for mixing the cyclic olefin polymer according to the present invention with other components, a method known per se can be applied, and for example, each component can be mixed simultaneously.

[Preparation of molded article] Various molded articles can be produced using the plating composition according to the present invention. For the preparation of these molded products, general molding methods known per se such as injection molding, extrusion molding, T-die molding, inflation molding, blow molding, rotational molding, foam molding, press molding, and vacuum molding are employed. can do. Further, there is no particular limitation on the form of the molded article thus prepared. For example, when a sheet or a film is prepared, the thickness thereof is appropriately determined according to the intended use.

[Type of Metal in Plating Layer and Plating Method] The plating layer applied to the surface of a molded article formed using the plating composition according to the present invention is made of a metal that can be used for industrial or decorative purposes. It is formed of a metal appropriately selected from among them. For example, examples of such metals include copper, nickel, silver, aluminum, and gold.

The thickness of the plating layer formed on the resin layer surface of the molded body is
Depending on the purpose of the molded product, it is usually 0.5 to 50μ
m.

There is no particular limitation on a plating method for forming a plating layer on the surface of the molded product, and a method such as a conductive paint method, a chemical plating method, a vapor deposition method, or a gas layer method is employed in consideration of the use of the plated product. be able to. For example, a metal can be laminated on the surface of a molded article by employing a chemical plating method. The plating layer does not need to be formed by a single method, and may be formed by, for example, a combination of an electroless plating method and an electrolytic plating method.

[Uses of plated products] The plated products manufactured as described above include front grills, wheel caps, door handles, mirror housings and the like for automobile parts, decorative housings for home appliances and office equipment, and electromagnetic wave shielding toys. However, the present invention is not limited to this.

Effect of the Invention As described above, by using the composition for plating according to the present invention, a plating layer can be favorably formed on the surface of a molded article prepared using the resin composition. The plated material is excellent in heat resistance, heat aging resistance, chemical resistance, boiling water resistance and impact resistance, and has high adhesion of the metal plating layer, so that it can be used for a wide range of applications.

Examples Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these examples.

The methods for measuring and evaluating various physical properties in the present invention are shown below.

(1) Flexural modulus; measured at a temperature of 23 ° C. by the method of ASTM-D790.

(2) Flexural strength: measured at a temperature of 23 ° C. according to the method of ASTM-D790.

(3) Izoto impact strength (with notch); temperature 23 ° C, 0
At -30 ° C, according to the method of ASTM-D256.

(4) Drop weight impact strength: measured at a temperature of 23 ° C., 0 ° C., and −30 ° C. according to the method of ASTM-D3029.

(5) Heat deformation temperature (HDT): Measured by the method of ASTM-D648 under the conditions of 4.6 kg / cm ² and 18.6 kg / cm ² load.

(6) Melt flow index (MFR T ° C): measured at a predetermined temperature T ° C according to the method of ASTM-D785.

(7) Plating property evaluation method (i) Cross cut test Using a cutter blade, a 1.5 mm width cross cut is made in the plating layer to a depth reaching the substrate. Adhere Scotch # 610 tape to the cross cut surface and perform a 90 ° peel test. The result is represented by the number of non-peeled pieces out of 100 grids.

(Ii) Adhesion test A 1 cm wide strip is cut using a cutter blade to a depth that reaches the substrate. A 180 ° peel test was performed from the end, and the result was expressed as stress per 1 cm width.

Example 1 Ethylene and 1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a, -octahydronaphthalene (DM
Called ON. ) (Intrinsic viscosity [η])
3.4 kg pellets with 0.6dl / g, Tg 122 ° C, MFR _{260 ° C} 15g / min. And softening temperature (TMA) 134 ° C; ethylene content 66mol%)
And [B] a low-crystalline α-olefin copolymer (ethylene-propylene random copolymer; ethylene content 80 mol%, intrinsic viscosity [η] 2.2 dl / g, Tg-54 ° C, MFR
After sufficiently mixing 0.6 kg of pellets at _{230 ° C with} 0.7 g / min., The mixture was melt-blended at a cylinder temperature of 220 ° C by a twin-screw extruder (PCM-45, manufactured by Ikegai Iron Works Co., Ltd.) and pelletized by a pelletizer.

Injection molding was performed on the obtained pellets under the following conditions to obtain a test piece for physical measurement.

Molding conditions After injection molding IS-50EP manufactured by Toshiba Machine Co., Ltd. Cylinder temperature 250 ° C., mold temperature 80 ° C. Injection pressure Primary / secondary = 1000/800 kg / cm ^{2 The} obtained test piece was plated according to the following method.

1. Specimens are degreased by immersing them in an aqueous solution of a neutral detergent at 50 ° C for 5 minutes. Then wash thoroughly.

2. The degreased test piece is immersed in the following chemical etchant at 75 ° C for 15 minutes to perform etching. Thereafter, it is sufficiently washed with a washing solution.

Chemical corrosion liquid composition Potassium dichromate 15 g Sulfuric acid 100 cc Water 50 cc 3 The etching test piece is immersed in the following sensitizer solution at room temperature for 3 minutes with stirring to perform sensitization treatment. Then wash thoroughly.

Sensitizer solution composition Stannous chloride 10 g Hydrochloric acid 40 cc Water 1000 cc 4 Sensitive treatment A test piece is immersed in the following activator solution for 1 minute at room temperature for activation treatment. Then wash thoroughly.

Activator solution Palladium chloride 1 g Hydrochloric acid 10 cc Water 1000 cc 5 Activated molded product is subjected to chemical copper plating at room temperature for 10 minutes using the following chemical copper plating solution. Thereafter, it is thoroughly washed.

Chemical copper plating solution composition Copper sulfate 15 g Rossel salt 120 g Sodium hydroxide 30 g Formalin 30 cc Water 1000 cc The results of measuring the physical properties of plating test pieces treated as described above are shown in Table 1.

Example 2 1 g of Perhexin 25B ^TM manufactured by NOF Corporation and 3 g of divinylbenzene were added to 1 kg of the pellet obtained in Example 1.
And mixed well. The mixture was reacted at a cylinder temperature of 230 ° C. while being melted by a twin-screw extruder, and pelletized by a pelletizer. Using the obtained pellets, test pieces were prepared and plated under the same molding conditions as in Example 1, and the results of measuring the physical properties of the plated test pieces treated as described above are shown in Table 1.

Example 3 Addition copolymer of ethylene and DMON as the component (A) (intrinsic viscosity [η] 0.47 dl / g, Tg 137 ° C, MFR _{260 ° C} 35 g / mi
n. and softening temperature (TMA) 148 ° C; ethylene content 62mol
%) Pellets and low-crystalline α-olefin copolymer (ethylene / propylene random copolymer; ethylene content 80 mol%, intrinsic viscosity [η] 2.2 dl / g, Tg-54 as component [B]) ° C, MFR
After sufficiently mixing with 0.6 kg of pellets ( _{230 ° C,} 0.7 g / min.), The mixture was melt-blended at a cylinder temperature of 220 ° C by a twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) and pelletized by a pelletizer.

To 1 kg of the obtained pellets, 1 g of Perhexin 25B ^™ manufactured by NOF Corporation and 3 g of vinylbenzene were added and mixed well. The mixture was reacted with a twin-screw extruder at a cylinder temperature of 230 ° C. while being melted, and formed into a penlet with a pelletizer. Using the obtained pellets, test pieces were prepared under the following conditions, and plated in the same manner as in Example 1.
Table 1 shows the results of measuring the physical properties of the plated test pieces treated as described above.

Molding conditions Cylinder temperature 250 ° C, mold temperature 90 ° C Injection pressure Primary / secondary = 1000/800 kg / cm ² Injection speed Medium speed Example 4 Ethylene used as the component [A] in Example 3
Instead of DMON addition copolymer, ethylene / DMON addition copolymer with ethylene content 71mol%, intrinsic viscosity [η] 0.6d / g, Tg98 ℃, MFR _{260 ℃} 20g / 10min. And softening temperature (TMA) 115 ℃ A mixture using 4 kg of the pellet and 1 kg of the pellet of the component [B] similar to that of Example 3 was molded into a test piece under the following molding conditions, and subjected to the same plating as that of Example 1. Table 1 shows the measurement results of the physical properties of the plated test pieces treated as described above.

Molding conditions Cylinder temperature 250 ° C., mold temperature 70 ° C. Injection pressure Primary / secondary = 1000/800 kg / cm ² Injection speed Medium speed Example 5 2.8 kg of resin pellets obtained in Example 4, magnesium hydroxide (Kyowa 1.5 kg of Kisuma 5A manufactured by Chemical Co., Ltd., 0.5 kg of decabromodiphenyl ether (Nonene DP-10F manufactured by Marubishi Yuka Co., Ltd.), 150 g of antimony trioxide, Teflon powder (Teflon 6J manufactured by Mitsui Crochemicals, Inc.) 50
After sufficiently mixing g, the mixture was melt-blended with a twin-screw extruder and pelletized with a pelletizer. A test piece was molded under the molding conditions of Example 4 and plated in the same manner as in Example 1 except that the etching conditions were changed to 55 ° C. for 10 minutes. Table 1 shows the results of measuring the physical properties of the plated test pieces treated as described above.

The resin before plating was UL-94 V-0 (thickness 1/16 inch) flame retardant.

Examples 6 to 10 Test pieces were plated in the same manner as in Example 3 except that the type of the component [B] was changed as shown below. Table 2 shows the results.

Ethylene / propylene random copolymer (ethylene content: 80 mol%, intrinsic viscosity [η]; 2.4 dl / g, Tg; -55 ° C) ... Example 6 Ethylene / propylene / ethylidene norbornene random copolymer Polymer (ethylene content: 67 mol%, ethylidene norbornene content: 3 mol%, intrinsic viscosity [η]; 2.2 dl / g, Tg; -45 ° C.) Example 7 ethylene propylene DMON random copolymer (ethylene content: 66 mol%, DMON content: 3 mol%, intrinsic viscosity [η]; 2.5 dl / g, Tg; -35 ° C.) Example 8 styrene. Hydrogenated product of isoprene / styrene block copolymer (styrene content: 30% by weight, intrinsic viscosity [η]; 0.65 dl / g, Tg; -58 ° C, 90 ° C) Example 9 Styrene / butadiene random Copolymer (styrene content: 30% by weight, intrinsic viscosity [η]; 1.5 dl / g, Tg; -57 ° C) ... Example 10 Comparative Example 1 An injection-molded product was produced using only the component (A) of the ethylene copolymer used in Example 1, and plating was performed in the same manner as in Example 1. However, the molded product could not be plated.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 47/00 C08L 47/00 53/02 53/02 65/00 65/00 C23C 18/16 C23C 18/16 A

Claims (2)

(57) [Claims] 1. A ring-opened polymer and a ring-opened copolymer of a cyclic olefin represented by the following formula [I], a hydrogenated product of the polymer and the copolymer, and a compound represented by the following formula [I] A cyclic olefin-based resin selected from the group consisting of an addition polymer of a cyclic olefin and ethylene, and 5 to 100 parts by weight of a soft polymer with respect to 100 parts by weight of the cyclic olefin-based resin; and The united product consists of (i) an ethylene component unit, an α-olefin component unit other than ethylene, and a cyclic olefin component unit represented by the following formula [I], and has an intrinsic viscosity [η] measured in decalin at 135 ° C. Is 0.01 to 10 dl / g and the glass transition temperature Tg is 0
(Ii) an amorphous or low-crystalline α-olefin copolymer having a glass transition temperature Tg of 0 ° C or lower formed from at least two kinds of α-olefins. (Iii) an α-olefin / diene-based copolymer having a glass transition temperature Tg of 0 ° C. or lower formed from at least two kinds of α-olefins and at least one kind of non-conjugated diene; (iv) glass transition An aromatic vinyl hydrocarbon / conjugated diene random or block copolymer having a temperature Tg of 0 ° C. or lower, or a hydride thereof; and (v) a soft polymer or copolymer comprising isobutylene or isobutylene and a conjugated diene. A composition for plating, which is at least one resin selected from the group consisting of: [In the above formula [I], n is 0 or a positive integer, and R ^{1 to} R ¹² each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group; R ^{9 to} R ¹² may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond; ⁹ and R ¹⁰ or R ¹¹ and R ¹² may form an alkylidene group]. 2. A plated article, characterized in that it has a metal plating layer on at least a part of the surface of a resin molded article made of the composition for plating according to claim 1.