JPH0314882A - Plating composition and plated object - Google Patents

Abstract

PURPOSE:To obtain the subject composition which gives a plated object excellent in resistances to chemicals, boiling water, aging and impact by using a specified cyclic olefin resin and a specified flexible polymer each in a specified amount as constituents. CONSTITUTION:The subject composition consists of 100 pts.wt. cyclic olefin resin (A) selected from a (hydrogenated) ring-opening (co)polymer of a cyclic olefin of the formula (wherein (n) is O or above; R<1> to R<12> are each H, halogen or hydrocarbon group, R<9> to R<12> may be combined together to form a monocyclic or polycyclic group, and R<9> with R<10>, and R<11> with R<12> respectively may form an alkylidene group) and its adduct with ethylene; and 5-100 pts.wt. of at least one flexible polymer (B) selected from a cyclic olefin random copolymer consisting of ethylene component units, other alpha-olefin component units, and units of a cyclic olefin component of the formula and having specified physical properties, a specified noncrystalline or lowly crystalline alpha-olefin copolymer, a specified alpha-olefin/diene copolymer, a specified (hydrogenated) aromatic vinyl hydrocarbon/conjugated diene random or block copolymer, and a flexible isobutylene (conjugated diene) (co) polymer.

Description

[Detailed Description of the Invention] The present invention relates to a plating composition and a plated article, and more specifically relates to heat resistance, chemical resistance, boiling water resistance, heat aging resistance and resistance to plating. The present invention relates to a resin assembly capable of forming a plated article with excellent impact resistance, and a metal plated article formed from this resin assembly.

Today's ``Resin products have been transformed to give them a metallic luster for decorative purposes.
Alternatively, the surface may be plated with metal to shield electromagnetic waves. Chemical plating methods, conductive paint methods, vapor deposition methods, vapor phase methods, and the like are known as methods for plating metal on the surface of resin shaped bodies.

By the way, the applicant has already filed an application for cyclic olefin resin as a resin with excellent heat resistance, heat aging resistance, chemical resistance, etc. (for example, If, JP-A-60-26
No. 024, No. 60-168708, No. 61-1159
(Refer to publications such as No. 12).

By providing a metal plating layer on the surface of such a cyclic olefin-based resin shaped body, it has excellent heat resistance, heat aging resistance, chemical resistance, etc. The surface has a metallic luster, and it also provides electromagnetic shielding. It is possible to obtain a precept form with excellent characteristics such as gender.

However, when metal plating is actually applied to such a cyclic olefin polymer, it may not be possible to easily form a shaped body formed from a cyclic olefin resin.

The present invention aims to provide a plateable resin composition containing a cyclic olefin polymer as a resin component.

Other objects of the present invention (transition) A molded article formed from a resin containing the above-mentioned resin composition has a metal plating layer formed on the surface, and has good heat resistance, heat aging resistance, chemical resistance, and boiling water resistance. and to provide plated products with excellent impact resistance.

41 The plating composition according to the present invention comprises: a ring-opening polymer of a cyclic olefin represented by the following formula [I], a ring-opening copolymer, a hydrogenated product of the polymer and copolymer, and the following formula [T]
A cyclic olefin resin (component [A]) selected from the group consisting of addition polymers of cyclic olefin and ethylene represented by: - the soft polymer force Z which is composed of a polymer ([B'l certain amount) and is this [B] certain amount
(i) Consisting of an ethylene minute unit, an a-olefin component unit other than ethylene, and a cyclic olefin minute unit represented by the following formula [2], the intrinsic viscosity measured in decalin at 135°C [7] is 0.01 to 10 dlA Cyclic olefin random copolymer with a glass transition temperature Tg of 0°C or lower; (ii) an amorphous copolymer with a glass transition temperature Tg of 0°C or lower formed from at least two types of σ-olefins; (iii) a glass transition temperature Tg formed from at least two types of a-olefins and at least one type of non-conjugated diene is 0°C;
(iv) an aromatic vinyl hydrocarbon/conjugated diene random or block copolymer having a glass transition temperature Tg of 0° C. or lower, or a hydride thereof; ) It is characterized by being at least one type of resin selected from the group consisting of isoptylene or a soft polymer or copolymer consisting of isobutylene and a conjugated diene.

...[I] In the above formula [tl, nllo or a positive integer, RI=Rl2 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R9 to R l 2 14 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond; or the R position and R+2 may form an alkylidene group.

Furthermore, the plated article according to the present invention is characterized in that it has a metal plating layer on at least a portion of the surface of a resin molded article formed from the above-mentioned plating composition.

The present invention (L) By blending a specific soft polymer with a cyclic olefin polymer that has excellent heat resistance, heat aging resistance, chemical resistance, and boiling water resistance, the adhesion between this resin and the plated metal is extremely good. This was made based on the knowledge that the present invention provides a plated product that can be used in a wide variety of applications.

Metal layer L as a plating layer of the present invention chemical plating method,
The shape is applied to the surface of the plating composition by a conductive paint method, vapor deposition method, vapor phase method, or the like.

However, for example, as shown in the comparative example described below, such a metal layer 1 can be completely changed when a cyclic olefin resin is used alone. Can not do it.

Therefore, the inventor of the present invention discovered that adhesion to metals could be improved by blending a specific amount of a cyclic olefin resin E as the [A] component and a specific soft polymer as the [B] component. Therefore, the plating composition IL of the present invention
[A1! Cyclic olefin resin &:, (i) ~
Component [B] of (v) is blended. This [B] precept,
[A] By blending the plating composition in an amount of 5 to 100 parts by weight per 100 parts by weight, the adhesion of the plating composition to the metal layer is significantly increased and a uniform metal layer is formed on the surface. Impact strength is also improved.

Note that the surface of the shaped body formed from the plating composition may be subjected to physical and chemical treatments such as mechanical treatment, chemical corrosion treatment, sensitization treatment, and activation treatment.

Since the [Al-containing] plating composition of the present invention improves the heat resistance, heat aging resistance, chemical resistance, and boiling water resistance of the plating composition, it improves the susceptibility of the resin to the mechanical treatment and chemical corrosion treatment described above. The assembly or material can be easily treated without causing excessive corrosion or the like. In addition, the metal of the plating layer is not limited to silver, nickel, etc., which can be used as industrial materials, but also decorative materials such as gold.

The following is a detailed explanation of the plating composition and plated article of the present invention.

[Cyclic Olefin Part] Plating composition 19 according to the present invention is composed of a cyclic olefin resin and a soft polymer.

Cyclic olefin resin 19 Formula [! ] Copolymers and their hydrogenated products, as well as copolymers formed by addition polymerization of cyclic olefins represented by the following formula [1] and ethylene. Selected from among resins consisting of copolymers.

may have. Furthermore, this monocyclic or polycyclic group may have a double bond. Furthermore, it may be a group in which these rings are combined.

That is, the above R● to RI2 may jointly form, for example, a polycyclic or monocyclic group as described below.

... [I] However, in the above formula [I], n is O or a positive integer, and R1 to R l 2 1 inversion are each independent &
represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, or a hydrocarbon group. Sara! :,
R @ -- R I 2 19 They may be bonded to each other to form a monocyclic or polycyclic group, and this ring forms a bridged structure, and in the above formula, 1 and 2 are added. carbon atom (9 In formula [1.], R @ − R
I represents a carbon atom in an alicyclic structure to which the group represented by 2 is bonded.

Furthermore, these groups may have a substituent such as a methyl group.

Furthermore, R● and Rl1 or R1@ and RI2 may form an alkylidene group. Furthermore, R
An ester group or the like may be included in 9 to RI2.

A preferable example of the taste of such a cyclic olefin is a cyclic olefin represented by the following formula [n].

...[n] However, in the above formula [nl, n is O or 1, m is O or a positive integer, and R1 to R I I +
k Each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Sara E, R I S - R I 11 1L
They may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond.

Furthermore, Rls and Rl6 or Rl and RI8 may form an alkylidene group.

In addition, an olefin polymer having an alicyclic structure (for example, a ring-opening polymer or an open-ring polymer obtained by ring-opening polymerization of the formula [nl] alone or in the presence of the formula [nl] as shown in the following formula) It may also be a ring copolymer.Furthermore, in the present invention, iL is a hydrogenated compound obtained by hydrogenating at least a part of the double bonds present in the above ring-opening polymer or ring-opening copolymer. You can also use objects.

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

The cyclic olefin represented by the above formula [r] used in the present invention includes 1-turn bicyclo[2,
2. 11Hepto-2-ene induced imitation tetracyclo[4
, 4, 0. 12・s, 1 cho・1●]-3-dodecene derivative hexacyclo[6, 6, 1. 1'・8,111+
3, Q2. ? ．． QQ. +4]-4-heptadensene derivative octacyclo[8, 8, 0. 12.9.14.7
．． 1st eye 1@, 113.1@, 03・s, Q+2. +7]
-5-docosene derivative, pentacyclo[6,6,1,1
3.1,0"・7,0●・+43-4-hexadecene derivative Imitation heptacyclo-5-icosene derivative Main heptacyclo-5-heneicosene derivative, tricyclo[4,3,0.12・S]-3-decene derivative,
Trisic mouth [4, 3, 0. 12.S]-3-undecene derivative pentacyclo[6, 5, 1. 13・
6, Q! ．． 'l, Q●・+3 ] −4
- Pentadecene induction This pentacyclobentadecadiene induction imitation 9 siku a [4,7,0.12-S,Q*Ii,
l●. +al-3-he:/tadecene-derived pentacyclo[7, 8, 0. 1'. 6,
02. ? , 11●. I? , QIl. l●. 11
2.II]-4-eicosene induced imitation and nonacyclo[9,10,1,1,4.7.0'1.02
-eye Ql 2 . 2 11+*. e@. 014.
1@, 1i s. + *1-5-Henta=r Se:/
One example is the tlt conductor.

Specific examples of such compounds are shown below.

Bicyclo[2, 2. 11 Hebuto 2-
Ene derivative; CH. C, H eyes 2, 7. 9- }Remethyltetra8-methyltetracyc8-ethyltetracyc1e-3-dodecene1@]-3-dodecene9-isobutyl11. 12 5, 8, 9. 10-tetramethy1@co-3-dodecene8-methyl-9-ethylte-3-dodecene-3-dodecene1@]-3-dodecene I●]-3-dodecene CH, 5.17 1●]-3- Dodecene 8-ethylidene-9-iso7.1●]-3-dodecene-dodecene-3-dodecene. 12 5,1 Te. +s]-3-dodecene. +1]-3-dodecene 5.17th]-3-dodecene 12. s. lll●] -3-dodece8-n-propylidene-9 -dodecene8-n-propylidene-9 8-isobropylidene [4, 4, 0. 12・s, 1〒 +@]-3 -dodecene-dodecene black [4, 4, 0. 12 17 1@]-3-dodecene+ 1 ]-3-dodecene 8-n-propylidene-9 [4, 4, 0. 12 5. Tetracyclo [4. 4, 0. 12・s. 1
D+@]-3-dodecene derivative 2・5.17・t●]-3-dodecene (blank below) 1-dodecene・+a]-4-heptadecene 1 2, Q2 7.09・+4]-4- Heptadecene etc. [6,6,1.1”.1””3,
02.7, O”decene+ − ]-4-hebutadecene derivative; 3.I a
, Q3. @ , Ql 2. I? ]
-5-desendocene 11.1$ 113.111,Qll,Qlhebutadecene2・+7]-5-desendocene+? ．． ]-5-docosene and other octacyclo[8, 8, O, l*. *
, 1'・7,1■1● 1+ 3.16,Q3. @, QI2.1'? ]-5-do=r-
1=N derivative;. @, Ql. pentacyclo [6, 6, 1. 13s, Q2. v,Q@+t]-4-hexadecene derivatives; tricyclo[4, 3, 0. 12・s]13
-Decene derivative; 1,6-dimethynolebenta-10-methyl-tricyl 14. Tricyclo[4, 4, 0. 12・S]13
- pentacyclo [6, 5, 1
．． 1'・la, Q2? , Q@. +3
] -4-body; Pentadecene derivative; Diene compounds such as; . 21.1I3.2● 0+4. +9.11th] - Pentacyclo such as 5-pentacosencene [4, 7, 0. 12・5.0●+z, 1e. +
a] -3-pentadecene derivative: 3.2@, QI4. I*, lIs. l@]-5-pentacocene and other nonacyclo[9, 10, 1. 14.7.03.8, O2th.
OI2 21.13 2●, O14 1● lIs. Ia] -5-pentacocene-derived cocene derivatives can be mentioned.

And 19 more ? ,11117,Qll +6,11 [S] -4-Eikosen Heptasic mouth such as [7, 13, Q, 11@, Q2. ? ,ILLS17,0 +8, lI2. Is] -4-eicosene derivative; can be mentioned.

Specifically as the polycyclic cyclic olefin represented by the formula [r] (also the above compound formula or 1, 4, 5. 8
-Dimethano-1. 2, 3, 4, 4a, 5,
8. In addition to 8a-octahydronaphthalene, 2-methyl-1. 4, 5. 8-dimethano-1. 2, 3,
4,4a, 5,8,8a-octahyde naphthalene, 2-ethyl-1. 4, 5. 8-dimethano-
1. 2, 3, 4, 4a, 5, 8, 8a-
Octahydronaphthalene, 2-probyl-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, 8
a-octahydronaphthalene, 2-bromo1. 4,
5. 8-dimethano-1,2,3,4,4a,
5. 8, 8a-octahyde naphthalene, 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-octahyde naphthalene, 2-n-butylene 1, 4, 5. 8-dimethano-1. 2, 3, 4, 4a, 5. 8.
8a-octahydronaphthalene, 2-isobutyl-1
, 4, 5. 8-dimethano-1. 2, 3, 4
, 4a, 5, 8, 8a-octahydronaphthalenes such as octahydronaphthalene can be exemplified.

[Cyclic olefin polymer: [A] Cyclic olefin polymer used in the plating composition of the present invention includes (1) a ring-opening polymer of a cyclic olefin represented by the above formula [r]; A combined or ring-opened copolymer or a hydrogenated product thereof, (2) the above formula [! ] Copolymers obtained by addition polymerization of a cyclic olefin and ethylene can be mentioned.

Cyclic olefin ring-opening polymer (transformation) A cyclic olefin represented by the above formula [I], preferably [■], is ring-opening polymerized by a method known per se, and is a product obtained by homopolymerization or copolymerization. Yes, even sleep 1, 4, 5. 8
-Dimethano-1. 2, 3, 4, 4a, 5,
A copolymer of 8, 8a-octahydronaphthalenes, or the above-mentioned norbornene (bicyclo[2.
2.1] hept-2-ene) may be copolymerized.

In the ring-opening polymer or ring-opening copolymer of a cyclic olefin as described above, for example, at least a portion of the cyclic olefin represented by the formula [n] has a structure represented by the following formula [m]. It is thought that there are.

As a result, hydrogenated products have better thermal stability and weather resistance.

In such a hydrogenated product, for example, at least a portion of a cyclic olefin represented by the formula [n], for example, the following formula [■
It is thought to have the structure shown below.

... [ml In addition, the ring-opening polymer can be easily hydrogenated by hydrogenating the remaining double bonds by a method known per se... [■] In the above formulas Cm] and [■, R1 ~RI* has the same meaning as in formula [m].

By the way, when ring-opening polymerizes a cyclic olefin, the above formula [
I], or preferably, other cyclic olefins may be ring-opened and copolymerized within a range that does not impair the physical properties of the ring-opened (co)polymer formed from the cyclic olefin represented by formula [■]. Examples of such cyclic olefins are cycloptene, cyclobentene, cyclohexene,
3.4-dimethylcyclobentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, 2, 3, 3a, 7a-tetrahydro 4.7
-methanol IH-indene and 3a, 5, 6,
7a-tetrahydride I: I-4. Examples include 7-methanol IH-indene.

In the cyclic olefin addition polymer, the ethylene fraction/cyclic olefin fraction (molar ratio) is usually 10/90 to 90/
10, preferably 50/50 to 75/25. Production of ethylene-based copolymers (also carried out by polymerizing ethylene and cyclic olefins in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound). The polymerization method is already known;
This method has been proposed in Publication No. 8708 and the like.

In addition, in the cyclic olefin addition polymer, in addition to the cyclic olefin component and ethylene component, α-olefin component and/or formula [1]
Alternatively, a random copolymer obtained by adding and polymerizing a certain amount of a cyclic olefin other than the cyclic olefin represented by [III] may be used in the plating composite according to the present invention.

As α-olefins (mu) linear or branched ones, such as propylene, l-butene,
-Methyl-■-A- with 3 to 20 carbon atoms such as -bentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene One can mention olefin. Among these (9 carbon atoms 3~
15, in particular 3 to IO a-olefins are preferred.O In addition, other cyclic olefins here refer to formula [I]
and [ml of a compound other than a cyclic olefin,
It is a broad concept that encompasses all compounds recognized as unsaturated polycyclic hydrocarbon compounds.

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

Furthermore, as a cyclic olefin other than the cyclic olefin represented by formula [I] or formula [n], compounds having two or more double bonds in the molecule can be used. When such a compound is used, even if the double bonds that are not used in the addition polymerization reaction remain, the intoxicating effect is still t. Hydrogenation is added to these double bonds for the purpose of improving the weather resistance of the large-sized body. You can also.

In the above-mentioned cyclic olefin addition polymer, for example, at least a part of the cyclic olefin represented by formula [1] (a structure represented by the ninth-order formula [V] is formed to form a polymer) It is thought that there are.

...[v] However, in the above formula [V], m and n and R
I,. ．． ．． R l River 4 has the same meaning as these in formula [1].

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

(1) Cyclic olefin ring-opening polymer and its hydrogenated product and (2) cyclic olefin addition polymer 1 described above
Intrinsic viscosity [vl] measured in decalin at 135°C is 0.01 to 10 dl/g, especially 0.01 to 10 dl/g. 05～to
dl/a More preferably, 0.08 to 8 d1/g.

These cyclic olefin polymers GL are generally amorphous or have low crystallinity, and are preferably amorphous.

In general, the degree of crystallinity measured by X-rays is less than 5%, and in most cases it is 0.
%, in many cases no melting point is observed using differential scanning calorimetry (DSC).

Other properties of such cyclic olefin polymers include high glass transition temperature Tg and high softening temperature (TMA). Glass transition temperature Tg is usually 50 to 230
°C, mostly measured within the range of 70-210 °C. Therefore, when used directly in shaped materials, the four-turn softening temperature is usually measured within the range of 60 to 240°C, and in most cases within the range of 80 to 220°C.

Also, the thermal decomposition temperature is 1'! L% 350-420°C, mostly in the range of 370-400°C.

As for mechanical properties, the flexural modulus is usually IX104~sxt
It is within the range of o▲kg/cm2, and the bending strength is usually 3
It is within the range of 00 to 1500 kg/cm2.

Moreover, the density of this composition is usually 0.86 to 1.
10 g/cm2, mostly 0.88 to 1.08 g
/am” range. Also, the refractive index (ASTM D5
42) is l. 47~l. 58, mostly 1.
48-1. It is within the range of 56.

As for electrical properties, the dielectric constant (IKHZ) measured by ASTM D150 is 1.5 to 3. O, mostly 1.9 to 2.6, dielectric loss tangent 9x10-4 to 8x10-
'Many are in the range of 3X10-4 to 9X1O bows.

[Soft Polymer; [B] Partial] By blending this soft polymer, the adhesion with the metal plating layer is improved. As soft polymers that can be used in the present invention, the following (1) to (v) are described below.
Examples include rubber-like substances selected from the group of

Soft polymer having a repeating unit derived from a cyclic olefin Ethylene and the cyclic olefin shown in the explanation of the cyclic olefin polymer (compound represented by formula [I], preferably formula [m]) and a-olefin component. As σ-olefins (f1 propylene, 1-butene, 4-methyl-1-butene, 1-hexene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1
-hexadecene, 1-octadecene, 1-eicosene, etc. Among these (9 carbon atoms 3 to 20
α-olefins are preferred.

Furthermore, cyclic olefins and/or cyclic dienes such as norbornene, ethylidene norbornene, and dicyclobentadiene can also be used.

In preparing the soft polymer (1) having repeating units derived from a cyclic olefin, ethylene is 40
It is used in a range of 98 mol% to 98 mol%, preferably 50 to 90 mol%. In addition, a-olefin is used in an amount ranging from 2 to 50 mol%; cyclic olefin is used in an amount ranging from 2 to 20 mol%;
Preferably it is used in an amount ranging from 2 to 15 mol%.

Soft polymer (i) 14 Unlike the cyclic olefin polymer of the above [A] IL portion, it has a glass transition temperature (Tg
) is below 0°C, preferably below -10°C, and 13
Intrinsic viscosity measured in decalin at 5°C [η is o. oi
~10 di/g, preferably 0.8-7 di/g
It is g. The soft polymer (1) has a crystallinity of O-to%, preferably O-7%, particularly preferably O-5%, as measured by X-ray diffraction.

This soft polymer (i) +& JP-A-60-1687
No. 08 Public/Private Unexamined Publication No. 6 1-1 208 1 No. 6 Public Unexamined Patent Publication No. 61-115912 Public/Private Unexamined Patent Application No. 61-115
No. 916 Public/Private JP-A-61-271308 Public-Aid JP-A-61-272216 Public-Private JP-A-62-25240
It can be manufactured by appropriately selecting conditions according to the method proposed by the present applicant in Publication No. 6 and the like.

a-olefin polymerization (11 α-olefin copolymer (ii)+4 used as a soft polymer An amorphous or low-crystalline copolymer consisting of at least two types of a-olefins.

Specific examples include 13 ethylene/α-olefin copolymer and propylene/a-olefin copolymer.

When preparing this ethylene/a-olefin copolymer, σ-olefins having 3 to 20 carbon atoms are usually used. Specifically, propylene, 1-butene, 4
-Methyl-1-butene, 1-hexene, 1-octene,
Examples include 1-decene a or a mixture thereof.

Among these, alpha-olefins having 3 to 10 carbon atoms are particularly preferred.

The molar ratio of repeating units derived from ethylene and repeating units derived from α-olefin in an ethylene/α-olefin copolymer (ethylene/α-olefin) 1 mo The force C, which varies depending on the type of α-olefin, Generally it is 40/60 to 95/5. Further, the above molar ratio is preferably 40/60 to 90/10 when the a-olefin is brobylene, and let, 50/50 when the α-olefin is an α-olefin having 4 or more carbon atoms. It is preferable that it is 95/5.

When preparing a propylene/a-olefin copolymer, an α-olefin having 4 to 20 carbon atoms is usually used. Specifically, 1-turn 1-butene, 4-methyl-1-bentene, 1-hexene, 1-octene, 1-decene a
Alternatively, a mixture thereof may be mentioned. For this tag, α-olefins having 4 to 10 carbon atoms are particularly preferred.

In the propylene/α-olefin copolymer described above, repeating units derived from propylene and a-
The molar ratio of repeating units derived from olefins (propylene/a-olefin) varies depending on the type of α-olefin.
It is.

α-olefin/diene copolymer (iii) used as a soft polymer (alpha-olefin/diene copolymer (iii))
Examples include 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, such as propylene, 1-butene, 1-bentene, 4-methyl-1-bentene, 1-hexene, Examples include 1-octene, 1-decene, and mixtures thereof. Among these (
Also preferred are a-olefins having 3 to 10 carbon atoms.

However, in the case of a propylene/α-olefin/diene copolymer, α-olefins having 14 carbon atoms and 4 to 20 are used.

In addition, the diene component i4 that composes these copolymer rubbers
1,4-hexadiene, 1,6-octadiene, 2
-Methyl-1,5-hexadiene, 6-methyl-1,5
- linear non-conjugated dienes such as hebutadiene and 7-methyl-1,6-octadiene, cyclohexadiene, dicyclobentadiene, methyltetrahydroindene, 5
-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-
Cyclic nonconjugated dienes such as 5-isoprobenyl-2-norbornene, as well as 2,3-diisopropylidene-5
- norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-probenyl-2.2-
Examples include norbornadiene.

The molar ratio of repeating units derived from ethylene and repeating units derived from α-olefin in the above ethylene/a-olefin/diene copolymer rubber (ethylene/α-olefin) + the type of Ca-olefin also differs. Normally 4 0/6 0-90/1
It is 0.

In addition, the content of repeating units derived from diene components in these copolymer rubbers is usually 1 to 20 mol%, preferably 2 to 15 mol%.

Aromatic vinyl hydrocarbons used as soft polymers
Conjugated diene-based soft copolymer (1) A random copolymer or block copolymer of an aromatic vinyl hydrocarbon and a conjugated diene-based compound, 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 repeating units derived from an aromatic vinyl hydrocarbon to repeating units derived from a conjugated diene (aromatic vinyl hydrocarbon/conjugated diene) is usually 10/90. ~70/30. Also, a hydrogenated copolymer rubber is a copolymer rubber in which part or all of the double bonds remaining in the above copolymer rubber are hydrogenated.

In-butylene-based soft polymer or copolymer (v) used as a soft polymer.Specifically, polyisobutylene rubber, polyisoprene rubber, polybutadiene rubber, in-butylene-isoprene copolymer rubber, etc. are used. .

In addition, the properties of the copolymers (11) to (v) which are soft polymers (9) are similar to the properties of the cyclic olefin-based soft polymer (i), and the properties of these soft polymers are measured in decalin at 135°C. Intrinsic viscosity ['7]IL usually 0.01~
10 dl/g, preferably within the range of 0.08 to 7 dl/H, and the glass transition temperature (TΦIL is usually O
C or lower, preferably -10C or lower, particularly preferably -20C or lower. Further, the degree of crystallinity measured by X-ray diffraction is in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

For 100 parts by weight of the cyclic olefin addition polymer, which is such a rubber-like substance ([B] substance) and [A] substance,
It is used in amounts 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 rubber-like Ibun ([B] Ibun) taka can be used alone or in combination of two or more types.

When using two or more types of rubber-like materials in combination,
The content of the rubbery components in the resin composition of the present invention is the total content of the rubbery components.

By controlling the content (total amount) of a certain amount of the soft polymer [B] in the resin composition of the present invention within the range of 5 to 100 parts by weight, the surface of a molded article manufactured from this resin composition can be improved. When it becomes possible to apply good plating to a common number;
The molded article has good impact strength, rigidity, and hardness, and the heat distortion temperature of the resin also falls within a good range.

That is, if the content of the soft polymer is much less than 5 parts by weight, it becomes difficult for plating to adhere to the surface of the shaped body, and the impact strength of the molded body tends to decrease. On the other hand, when the amount of the soft polymer greatly exceeds 100 parts by weight, the heat distortion temperature of the resin composition tends to be low, and the rigidity and hardness of the shaped body tend to decrease.

Resin composition of the present invention (9) As described above, the composition C1 is a composition containing a cyclic olefin polymer and a soft polymer.
A crosslinked structure may be present in this composition. That is, even if the composition of the present invention consisting of a component [A] of a cyclic olefin polymer and a component [B] of a soft polymer, a crosslinked structure is formed using an organic peroxide. By using a crosslinked polymer alloy prepared in this way (crosslinked polymer alloy), it is possible to form a molded article with a particularly excellent balance of properties such as plating properties, impact resistance, and heat distortion temperature. A composition can be obtained.

An example of an organic peroxide used in this case is +4
Ketone peroxide plasma such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t
-butylperoxy)cyclohexane 2,2-bis(t
-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3.3-tetramethylbutylhydro Hydroperoxide melon such as peroxide Di-t-butyl peroxide, 2.5-dimethyl-2.5-
Di(t-butylveroxy)hexane, 2,5-dimethyl-2,5-di(t-butylveroxy)hexyne-3
Diasilver oxide such as dialkyl peroxide, lauroyl peroxide, penzoyl peroxide etc.
Examples include peroxy esters such as t-butyl peroxy acetate, t-butyl peroxy benzoate, and 2.5-dimethyl-2.5-di(penzoyl peroxy)hexane.

The organic peroxide component is usually 0.01 to 1 part by weight, preferably O. It is used within the range of OS to 0.5 parts by weight.

When shaping the crosslinked structure as described above, a compound having two or more radically polymerizable functional groups in the molecule may also be blended. By eliminating compounds having two or more radically polymerizable functional groups in the molecule, crosslinking efficiency can be increased.

The radically polymerizable functional group used here is contained within the molecule.
Examples of compounds containing more than 100% of the total amount of divinylbenzene, vinyl acrylate, vinyl methacrylate, etc. , usually 1 part by weight or less, preferably 0.1-0.
It is used in an amount of 5 parts by weight.

[Other Additives] Inorganic fillers can be added to the plating composition according to the present invention. The inorganic filler reacts with or dissolves in the etching solution during the etching process during plating, thereby making it more efficient for the etching solution to adjust the surface condition of the shaped body. Examples of inorganic fillers that can be used here include wollastonite, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

The blending amount of the filler is usually 100 parts by weight or less per 100 parts by weight of the total amount of [A] Arubu and CB] Kaibu,
Preferably it is 5 to 50 parts by weight.

The plating composition according to the present invention also includes heat resistance stability II, weather resistance stability L, antistatic I1, slip resistance L, anti-blocking resistance L, anti-fog resistance L, smooth resistance L, within a range that does not impair the purpose of the present invention. Dyes, pigments, natural waxes, organic or inorganic fillers, etc. can be added.

Examples of stabilizers that may optionally be added include (L) tetrakis[methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)probionate]methane, β-(3.5-di-t-t) - Phenolic antioxidants such as butyl-4-hydroxyphenyl)probionic acid alkyl ester and 2,2-oxamidobis[ethyl-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate, stearic acid substituent
fatty acid metal salts, such as calcium stearate and calcium 1,2-hydroxystearate; Examples include alcohol fatty acid esters.

These may be blended alone or in combination. When blending in combination, for example, tetrakis[methylene-3-(3.5-di-t-butyl-4
-hydroxyphenyl)probionate] A combination of methane, zinc stearate, and glycerin monostearate, and the like.

We also use organic or inorganic fillers such as 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 flakes, glass beads,
Calcium silicate, montmorillonite, bentonite,
Examples include graphite, aluminum powder, molybdenum sulfide, Teflon powder, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers.

As a method for mixing the cyclic olefin polymer according to the present invention with other fractions, a method known per se can be applied, for example, each fraction can be mixed at the same time.

[Ij. Preparation of Shape Various molded articles can be manufactured using the plating composition according to the present invention. In the preparation of these products, injection molding, extrusion molding, IT die, and inflation are completed.
It is possible to adopt a general shaping method known per se, such as blowing, rotating, blowing, blowing, blowing, and vacuum shaping. There is no particular restriction on the form of the molded article prepared in this manner, and for example, if a sheet or film is prepared, the thickness thereof may be determined as appropriate depending on the intended use.

[Type of metal of the plating layer and plating method] The plating layer applied to the surface of a shaped product formed using the plating assembly according to the present invention can be used for industrial, decorative, etc. purposes. It is shaped by a metal selected appropriately from among metals. Examples of such metals include nickel, silver, aluminum, and gold.The thickness of the plating layer formed on the surface of the resin layer of the molded product also depends on the purpose of the molded product. Different power ξ Usually 0
．． It is in the range of 5 to 50 ln.

There are no particular restrictions on the plating method for forming a plating layer on the surface of the precept, and methods such as conductive paint method, chemical plating method, vapor deposition method, vapor layer method, etc. may be adopted in consideration of the intended use of the plated product. be able to. Example 1: By employing chemical plating, metal can be layered on the surface of a certain shaped product. Further, the plated layer 19 does not need to be formed by a single method; for example, it can be formed by a combination of electroless plating and electrolytic plating.

[Applications of plated products] The plated products manufactured as described above are used for automobile parts such as front grills, foil caps, door handles,
There are mirror housings, decorative housings for home office automation equipment, toys for electromagnetic shielding, etc.
, but is not limited to this.

As explained above, by using the plating composition according to the present invention, it is possible to form the plating layer well on the surface of the shaped body prepared using this resin composition. can. This plated product has excellent heat resistance, heat aging resistance, chemical resistance, boiling water resistance, and shock resistance, and since the metal plating layer has high adhesion, it can be used in a wide range of applications.

EXAMPLES 1 Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

The methods for measuring and evaluating various physical property values in the present invention are as follows: (1) Flexural modulus: ASTM-D
790 method.

(2) Bending strength: ASTM-D at a temperature of 23°C
790 method.

(3) Izoto impact strength (notched); temperature 23℃, O
℃, -30℃, measured by the method of ASTM-D256.

(4) Falling weight impact strength: Measured according to ASTM-D3029 at temperatures of 23°C, 0°C, and -30°C.

(5) Heat distortion temperature (HDT); 4. 6kg/
as21 8. Measured according to ASTM-D648 under a load of 6 kg/cm2.

(6) Melt flow index (MFRTt); Predetermined temperature T°C
Measured by ASTM-D785 method.

(7) Plating property evaluation method (1) Cross cut test Using a cutter blade, make a 1.5 mm wide cross cut in the plating layer to a depth that reaches the substrate.

Glue Scotch #610 tape to the cross-cut surface L,
, 90" peeling test is performed. The results are expressed as the number of non-peeling pieces in 100 pieces of a grid.

(1l) Adhesion Test Using a cutter blade, make a strip-shaped incision with a width of 13 to a depth that reaches the substrate. A 180° peel test is performed from the end, and the results are expressed as stress per 1 cm width.

1 yen [A] Ethylene and 1. 4, 5. 8-dimethano-1. 2, 3, 4, 4a, 5, 8,
Random copolymer with 8a,-octahydronaphthalene (hereinafter referred to as DMON) (intrinsic viscosity [v] 0
．． 6dl/g, Tg 1 2 2℃, M F
R 2 as 'c 1 5 g/min. and softening temperature (TMA) 134°C; ethylene content 66mol%
)'s beret 3. 4 kg, and [B] low crystalline α-olefin copolymer (
Ethylene/propylene random copolymer; ethylene content 80 mol%, intrinsic viscosity [η] 2.2 di/g, T
g-5 4°C, MF Rass Oe 0.
7 g/min. )'s beret 0. After thoroughly mixing 6 kg of
) was melt-blended at a cylinder temperature of 220°C and made into a pellet using a beletizer.The resulting bereft was then injection-shaped under the following conditions to obtain a test piece for physical measurement. IS-50EP cylinder temperature 250℃, mold temperature 80℃ injection pressure primary/secondary =
1000/800kg/. 2 The obtained test piece was plated according to the following method. 1 The test piece was immersed in an aqueous solution of a neutral detergent at 50°C for 5 minutes to degrease it. Then wash thoroughly with water.

2. Etch the degreased test piece by immersing it in the following chemical etching solution at 75°C for 15 minutes. Then wash thoroughly with cleaning solution.

Chemical corrosive solution: Potassium chromate 15 g Sulfuric acid 100 cc Water 50 cc 3 An 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 with water.

Sensitizer solution composition: Stannous chloride 10 g Hydrochloric acid 40 cc Water 1000 cc 4 The sensitivity treatment test piece is immersed in the following activator solution at room temperature for 1 minute to activate it. Then wash thoroughly with water.

Activator liquid Palladium chloride 1 g Hydrochloric acid 10 cc Water 1000 cc 5 Chemical steel plating is applied to the activated shaped product for 10 minutes at room temperature using the following chemical copper plating solution.

Then wash thoroughly.

Chemical steel plating solution or sulfuric acid steel 15g Rossel's salt 120g Sodium hydroxide 30g Formalin 30cc Water 1000cc Table 1 shows the results of measuring the physical properties of the plated test pieces treated as described above.

Nippon Oil & Fats for 1 kg of belene obtained in Example 1
Made by Perhexine 25BT! Add 1 g of I at a ratio of 3 g of divinylbenzene and mix thoroughly. This mixture is melted using a twin-screw extruder at a cylinder temperature of 230°C, reacted, and made into pellets using a pelletizer. Table 1 shows the results of measuring the physical properties of the plated test piece prepared and plated under the same conditions as in Example 1 and treated as described above.

Addition copolymer of ethylene and DMON (intrinsic viscosity [7] 0.47 dl/g, Tg1
37°C, MFR2. , oc35 g/mi
n. and softening temperature (TMA) 148°C, ethylene content 62 mol%). 4 kg, and [B] a portion of low crystalline a-olefin copolymer (
Ethylene/propylene random copolymer; ethylene content 80 mol%, intrinsic viscosity [η] 2.2 di/K,
Tg - 5 4℃, MFR 2311 0CO.
7g/min. )'s beret 0. After thoroughly mixing 6 kg of
The mixture was melt-blended at a cylinder temperature of 220°C and made into pellets using a pelletizer.For 1 kg of the obtained pellets, 1 g of Verhexin 25BT" manufactured by NOF Corporation, 1 g of vinylbenzene was added.
This mixture was melted using a twin-screw extruder at a cylinder temperature of 230°C, and then made into pellets using a pelletizer. Using the obtained pellets, test pieces were prepared under the following conditions. Table 1 shows the results of measuring the physical properties of plated test pieces that were plated in the same manner as in Example 1 and treated as described above.

Forming conditions Cylinder temperature 250℃, mold temperature 90℃ Injection pressure Primary/Secondary = 1000/800kg/. 32 Injection speed Medium speed Example 4 Ethylene/D used as [A] in Example 3
Instead of MON addition copolymer, ethylene content 71 mol
%, intrinsic viscosity [leverage 0. 6 d/g, Tg98℃,
MF R 26, oc 20g / 10mi
n. and softening temperature (TMA) 1 1 A mixture of 4 kg of ethylene/DMON addition copolymer pellets at 5°C and 1 kg of pellets of component [B] similar to those in Example 3 was prepared as a test piece under the following conditions. Table 1 shows the results of measuring the physical properties of a plated test piece that was plated in the same manner as in Example 1 and treated as described above.

Certain conditions Cylinder temperature 250℃, mold temperature 70℃ Injection pressure Primary/Secondary = 10007 800kg/Yo. Injection speed: Medium-speed cylinder 1'' 1.5 kg of the resin obtained in Example 4 2.84 magnesium hydroxide (Kisuma 5A manufactured by Kyowa Kagakuichi),
Decabromodiphenyl ether (Nonne DP-10F, manufactured by Marubishi Yuka ■) 0. 5 hidden antimony trioxide 15
0g, Teflon powder (manufactured by Mitsui Kurochemical)
After thoroughly mixing Teflon 6J) 50ge, it was melt-blended using a twin-screw extruder and made into pellets using a pelletizer.
Table 1 shows the results of measuring the physical properties of a plated test piece that was plated in the same manner as in Example 1 except that the temperature was changed to 5° C. for 10 minutes and treated as described above.

The resin before plating is UL-94 V-0 (1/16 inch thick) flame retardant. The test piece was plated using the same procedure except that the type of material was changed.
The results are shown in Table 2.

Ethylene-propylene random copolymer (ethylene content: 80 mol%, intrinsic viscosity [η]: 2, 4 dl/Koshiki Tg; -55
℃)...Example 6 DMON content; 3 molar limiting viscosity ['7]; 2. 5dl/fuTg;-3
5℃)...Example 8 Hydrogenated styrene-isoprene-styrene block copolymer (styrene content: 30% by weight, intrinsic viscosity [η]: 0.65 dl/fTg; -s
s°C, 90°C)...Example 9 Ethylene Propylene
Ethylidene norbornene random copolymer (ethylene content: 67 mol%, ethylidene norbornene content: 3 mol%, intrinsic viscosity [t7]. 2.2 dl/fTg; -45°C)
...Example 7 Styrene-putadiene random copolymer (styrene content: 30 weight limit viscosity [wa]; 1.5 dl/g.Tg; -5
7℃)...Example 10 Ethylene Propylene
DMON random copolymer (ethylene content: 66 mol%, Table 2) Injection molded products were prepared using only the [A] content of the ethylene copolymer used in Example 1. Plating is carried out using the same procedure as in Example 1.

Claims (2)

[Claims] (1) Ring-opened polymers, ring-opened copolymers of cyclic olefins represented by the following formula [I], hydrogenated products of the polymers and copolymers, and cyclic olefins represented by the following formula [I] a cyclic olefin resin selected from the group consisting of addition polymers of and ethylene, and the cyclic olefin resin 100
5 to 100 parts by weight of a soft polymer, and the soft polymer comprises (i) an ethylene component unit, an α-olefin component unit other than ethylene, and the following formula [I]: A cyclic olefin-based random copolymer consisting of the cyclic olefin component unit represented by the following formula, having an intrinsic viscosity [η] of 0.01 to 10 dl/g as measured in decalin at 135°C, and a glass transition temperature Tg of 0°C or lower. , (ii) an amorphous or low crystalline α-olefin copolymer with a glass transition temperature Tg of 0° C. or less formed from at least two types of α-olefins, (iii) at least two types of α-olefins. and at least one non-conjugated diene, and (iv) an aromatic vinyl having a glass transition temperature Tg of 0°C or lower. At least one resin selected from the group consisting of a hydrocarbon-based random or block copolymer, or a hydride thereof, and (v) a soft polymer or copolymer consisting of isobutylene or isobutylene and a conjugated diene. A plating composition characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the above formula [I], n is 0 or a positive integer, and R^1~ R^1^2 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R^9 to R^1^2 are bonded to each other to form a monocyclic or polycyclic ring. may form a ring group, and the monocyclic or polycyclic group may have a double bond, and R^9 and R^1^2 or R^1 ^1 and R
may form an alkylidene group with ^1^2]. (2) A plated article comprising a metal plating layer on at least a part of the surface of a resin molded article made of the plating composition according to claim 1.