JPH0395235A - Resin molding and method for treating it - Google Patents

Abstract

PURPOSE:To improve the adhesiveness and coatability of a molding without deteriorating the excellent characteristics of resin by applying a plasma to a surface of a molding of a specified cyclic olefin resin. CONSTITUTION:A plasma is applied to a surface of a molding comprising at least one cyclic olefin resin selected from a (hydrogenated) ring-opening (co)polymer, formed by the ring-opening polymerization of a cyclic olefin of the formula (wherein (n) is 0 or 1; (m) is 0 or greater, R<1> to R<18> are each H, halogen or a hydrocarbon group, wherein R<15> to R<18> may be combined to form a monocyclic or polycyclic, or R<15> and R<16> or R<17> and R<18> may form alkylidene), a modified derivative thereof, a (modified) copolymer of ethylene with the cyclic olefin of the formula, and a composition consisting of the aforementioned (hydrogenated) ring-opening (co)polymer, copolymer or modified derivative and other resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating the surface of a molded article made of a cyclic olefin polymer, and a resin molded article obtained by this method. More specifically, the present invention relates to a method for treating the surface of a shaped body made of a cyclic olefin polymer so that it has good adhesion or paintability, and a resin shaped body obtained by this method.

3-chain cyclic olefin polymer 1 conversion Excellent properties such as transparency, heat resistance, chemical resistance, electrical properties, mechanical strength, and formability The pre-shaped body has excellent dimensions It also has stability.

However, although this cyclic olefin polymer IL has excellent properties as described above, it is difficult to say that it has good adhesion to other materials, especially other resins or metals. Therefore, it is necessary to improve the adhesion properties when using cyclic olefin polymers, and the present invention is intended to solve the above-mentioned problems when using cyclic olefin polymers. It is a thing,
To provide a method for imparting excellent adhesion or paintability to a molded article without impairing the excellent characteristics inherently possessed by a cyclic olefin polymer, and to provide a molded article endowed with adhesiveness and paintability. It is an object.

Emitateka 1 Method for treating resin molded articles according to the present invention Ring-opening polymers or ring-opening copolymers formed by ring-opening polymerization of cyclic olefins represented by the 44th formula [+], and hydrogenated products thereof and copolymers of these modified diethylenes and cyclic olefins represented by the following formula [I], and modified products thereof, as well as the ring-opening polymers, ring-opening copolymer imitators, hydrogenated products, copolymers, or these. The method is characterized in that the surface of a molded article made of at least one type of cyclic olefin resin selected from the group consisting of a composition of a modified polymer of the above and another resin is brought into contact with plasma.

[I] However, in the above formula [I], n is 0 or 1, m is O or a positive integer, and R 14 R I I
Each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. and the monocyclic or polycyclic group may have a double bond, and
Ras and RI@ or Rl▼ and Rill may form an alkylidene group.

In addition, the resin molded product according to the present invention may be a ring-opening polymer formed by ring-opening polymerization of a cyclic olefin represented by the above formula CI] or a ring-opening copolymerization imitation thereof, a hydrogenated product thereof, a modified perethylene perethene thereof, and the above-mentioned Compositions of copolymers with cyclic olefins represented by formula [I], modified polymers thereof, ring-opening polymerized intercyclic copolymers, hydrogenated polymeric copolymers, or modified products thereof and other resins It is characterized in that the surface of the shaped body made of at least one type of cyclic olefin resin selected from the group consisting of:

According to the method of the present invention 1! Because the surface of the shaped body made of a specific cyclic olefin resin is brought into contact with plasma, this shaped body has excellent adhesion and coating properties without impairing the excellent properties originally possessed by the above-mentioned cyclic olefin polymer. can be given gender.

The processing method according to the present invention and the resin shaped body obtained by this processing will be specifically explained.

(a) Ring-opening polymer or ring-opening copolymerized vermilion formed by ring-opening polymerization of the cyclic olefin represented by the above formula [I] used in the treatment method according to the present invention. b) A copolymer of ethylene and the above cyclic olefin represented by [xl (hereinafter sometimes referred to as "cyclic olefin random copolymer"), (C) above (a) and (
b) a modified resin represented by (d) a ring-opening copolymer mimicking the ring-opening polymerization, a hydrogenated product,
It consists of at least one type of cyclic olefin resin selected from the group consisting of a cyclic olefin random copolymer or a modified product of this copolymer and another resin.

The cyclic olefin represented by the above formula [I1] can be easily produced by condensing cyclobentadiene and a corresponding olefin by a Diels-Alder reaction.

Specifically, examples of the cyclic olefin represented by the formula [xl include bicyclo[2, 2. 11 Hepto 2-
Ene derivative; 9-isobutyl-2,7-9, 11. 12-trimethylceneC Hs 5,10-dimethyltetra9-isobutyl11. 12 5, 8, 9. 10-tetrametinuma & waida total 1 blade and 8-methyltetrasic 8-ethyltetrasic + 1]-3-dodecene 8-hexyltetracyC + sH Lu, 1 @ ]-3-dodecene and 0 pieces total 1 blade Y & Kos. 17 +II]-3-dodecene+11]-3-dodecene-3-dodecene1 @ ]-3-dodecene. 12 s, 1 +1]-3-dodecene 8-methyl-9-ethylte=3-dodecene-3-dodecene19 3-dodecene+a]-3-dodecene aI←CE9 8-ethylidene-9-iso-dodecene, 12 5,1 knife 1 @]-3-dodecene 5,1 I]-3-dodecene 8-n-propylidene-9-dodecene swamp moth $4 blades in total 8 -n-propylidene 10t0Yutamine moblade 8-isopropylidene-dodecene-dodecene 1]-3-dodecene Is]-3-dodecene 8-n-propylidene-9-dodecene-dodecene etc. tetrasic group [ 4, 4, 0. 125.17
- II co-3-dodecene derivative; (blank below) 8-isopropylidene 14-4-heptadecene 12-methylhexacyc + s, Q2. v. Qs 4] Hexasic groups such as -4-heptadecene [6, 6. 1. 138.11
113, Q2. ? , QQ decene+i]-4-heptadecene derivatives: desendococene III, 113 + 8, Q3 @, Ol heptadecene 1 〒co-5-dococene 15-ethyloctacyc 1〒]-octacyclo[:8, 8 , 0. 12.9.
147, 11 1 +I, II 3. +6, Q3. *, Ql2 1〒]-5-docosene derivative; heptacyclo[8, 7. 0 Hebutacyclo-5-icosene derivatives such as cosene or hebutacyclo-5-heneicosene derivatives, etc.
a]-4-hexadecene derivatives; tricyclo[4, 3, 0. 1”s] 13-
Decene derivative; 1,6-dimethylbenta10-methyl-trisic14. Tricyclo[4, 4, 0. 1”・s]-3
- pentacyclo [6, 5, 1
．． 13-6 (p.?, Q*1 3 ] -4
- body; pentadecene derivatives; diene compounds such as 21,l+3.2@,Qlii,11S・l]-5-pentacosensenato+7)t:/9 sik o [4,7,0,if
',O"-",1"."]-3-pentadecene derivative; Cosene 121,QI4. l● ljs. I8] nonacyclo [9. lQ,l. l4.7,Qll,
Q2. ll, Ql221, 1st, gs. 0+a. +s,
1ta. +s] -5-hen9 Kose:/ derivatives can be mentioned.

(Left below) Heptacyclo[7,8,0.13・6.02・?2・+s]-4-eicosene etc.
Jl●・17.011. +16. ll2. Ill] -
4-eicosene derivative: used in the present invention (a
) The ring-opening polymer or ring-opening copolymer formed by ring-opening polymerization of the cyclic olefin represented by the formula [I1]
A cyclic olefin represented by, for example, ruthenium,
It is obtained by ring-opening polymerization in the presence of a catalyst consisting of a halide, nitrate or acetylacetone compound of a metal such as rhodium, palladium, osmium, indium or platinum, and a reducing agent such as an alcohol. These may be homopolymers or copolymers of cyclic olefins. For example, if 1,4,5.8-dimethano-1. 2, 4, 4a, 5, 8, 8a
Examples include those obtained by polymerizing two octahyde naphthalenes, and those obtained by copolymerizing the above-mentioned naphthalenes with norbornene (for example, bicyclo[2,2.13hept-2-ene).

The double bond 14 remaining in the ring-opened polymer or copolymer described above can be easily hydrogenated using a known reduction catalyst. In the present invention, such hydrogenated substances can also be used. Such hydrogenated products have excellent thermal stability and weather resistance.

In addition, when performing ring-opening polymerization, a cyclic olefin other than the cyclic olefin represented by the above formula [I] can be subjected to ring-opening polymerization within a range that does not impair the properties of the resulting polymer. Such cyclic olefins include cyclobutene, cyclobentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2
-(2-methylbutyl)-1-cyclohexene, 2,
Examples include 3,3a,7a-tetrahydro-4,7-methanol IH-indene and 3a,5,6,7a-tetrahydro-4,7-methanol IH-indene. Such other cyclic olefins alone are
Or it can be used in combination, usually 0 to 2
It is used in an amount of 0 mol%.

(b) Cyclic olefin random copolymer used in the present invention Obtained by copolymerizing ethylene and a cyclic olefin compound.

In the cyclic olefin random copolymer, the molar ratio of ethylene fraction to cyclic olefin fraction; usually 10:
90 ~90: 10, good mat, <ha 50:50
~75:25. Cyclic olefin random copolymer one-turn ethylene and cyclic olefin,
It can be produced by polymerization in a hydrocarbon solvent in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminium compound.

As the hydrocarbon solvent used in the present invention, for example, aliphatic hydrocarbon milk, alicyclic hydrocarbons, aromatic hydrocarbons, etc. can be used.

Furthermore, among the monomers used in the preparation of the cyclic olefin random copolymer, compounds that are liquid at the reaction temperature can also be used as the reaction solvent. These solvents can be used alone or in combination.

In the present invention, examples of the vanadium compound used as a catalyst include compounds represented by the i-transformation formula VO (OR), V, or the formula V (OR)cX. In the above formula, R is a hydrocarbon group,
05a≦3, o≦b≦3, 2≦a+b≦3, O≦C≦
4, O≦d≦4, 3≦c+d≦4. These vanadium compounds can be used alone or in combination.

Such a vanadium compound IL may be an adduct of a vanadium compound represented by the above formula and an electron donor.

In addition, examples of electron donors that form adducts with the above vanadium compounds include alcohols, phenolic ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, etc. Nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates may be mentioned. These electron donors 19 can be used alone or in combination.

As the organoaluminum compound used as a catalyst together with the vanadium compound as described above, a compound having at least one AQ-carbon bond in the molecule can be used.

Examples of organoaluminum compounds that can be used in the present invention include (i) Formula R's AQ(OR") nHt
Hydrocarbon groups containing 4 carbon atoms may be the same or different from each other. X is halogen, m is O≦m≦3, n is O≦n<3, p is O≦n<3, q is O≦q<3, and m + n + p + q=3. The organoaluminum compound represented by formula (11) MIAQRI
4 (wherein M1 is Li, Na, or K, and R1 has the same meaning as above), complex alkylated products of Group 1 metals and aluminum can be mentioned.

The concentration of the vanadium compound in the reaction system is usually 0.
, 01-5 gram atoms/9, preferably O. OS~3
It is used in an amount of gram atom/9.

In addition, the ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (i/V)
is 2 or more, preferably 2 to 50, particularly preferably 3 to 2
It is used in an amount that makes it 0.

Such a polymerization method itself is already known, and is described, for example, in Japanese Patent Application Laid-Open No. 168708/1983.

One layer of cyclic olefin random copolymer as mentioned above.
Other components such as a-olefin may be polymerized within a range that does not impair the properties of the polymer.

Such olefins include propylene, 1-butene, 4-methyl-1-bentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1
- An α-olefin having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms, particularly preferably 3 to 10 carbon atoms, such as eicosene, is used. A like this
-Olefins are usually used in amounts of 0 to 20 mol%.

In addition, as the cyclic olefin component, the component represented by the above formula [IF] is cycloptene, cyclopentene, cyclohexene, 3.
4-dimethylcyclohexene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene,
Cyclooctene and cycloolefins such as 3a, 5, 6, 7a-tetrahydro-4,7-methanol IH-indene;
n-butylnorbornene-2, 5-i-butylnorbornene 5.6-dimethylnorbornene 5-chloronorbornene Norbornenes such as 2-fluoronorbornene-2 and 5,6-dichloronorbornene-2, and styrene and methylstyrene etc. can also be used. Such compounds are usually used in amounts of 0 to 20 mol%.

Saraiso Cyclic olefin random copolymer 8 The cyclic olefin represented by formula [I] may contain a ring-opened repeating unit or a repeating unit derived from a hydrogenated product thereof.

In addition, other than the cyclic olefin represented by formula [I] & to 1
．． 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclobentadiene, 5-ethylidene-2
Compounds having two or more double bonds in the molecule, such as non-conjugated dienes such as mono-norbornene and 5-vinyl-2-norbornene, can also be used as they are or after being partially hydrogenated.

Furthermore, the intrinsic viscosity of the cyclic olefin random copolymer used in the present invention measured in decalin at 135°C is usually 0.01 to 20 dl/g, preferably 0.
．． 05 to 10 dl/koshi, more preferably 0. 08
It is within the range of ~8dl/g, and it is also within the range of thermal mechanical analyzer (TMA, Thermo-mech
using an anical analyzer), load 49
g, quartz needle (diameter 0.635 fine), quartz needle was heated to 0.635°C under the condition of temperature increase rate of 5°C/min. 1 - Softening temperature measured as the temperature at which it penetrates into the resin 1mm Usually 7
The glass transition temperature (Tg) is usually in the range of 50-230°C, preferably 70-210°C, measured by xH diffraction method. The degree of crystallinity obtained is usually 5% or less, preferably substantially 0%.

In addition, the thermal decomposition temperature of this copolymer is usually 350 to 4
It is within the range of 20°C, preferably 370-400°C.

The flexural modulus of this copolymer is usually 30.
It is within the range of 0 to 1500 kg/cm2, and the density is usually 0. 86-1. 1 og/cnf, preferably 0.88-1. It is within the range of 0.8g/cm, and the refractive index (ASTM D542) 1 inversion is usually 1.47~
l. 58, preferably within the range of 1.48 to 1,56, and since it is substantially amorphous, haze: A
STM 1003) 1 turn Usually 20% or less, preferably 10% or less.

As for the electrical properties of this copolymer, ASTMDI 50
The dielectric constant (l kHz) measured by L is usually 1. 5 to 3.0, preferably 1.9 to 2.6, and the dielectric loss tangent is usually in the range of 9X10-4 to 8X10-', preferably 3X10'' to 9X1O-'.

(C) Modified product of the resin described in (a) and (b) above used in the present invention. Ability to modify using β-unsaturated carboxylic acid button and/or its derivatives＼ Modify using styrenic hydrocarbon or organosilicon compound or unsaturated epoxy with olefinic unsaturated bond and hydrolyzable group Obtained by modification using a monomer.

σ, β-monounsaturated carboxylic acid and/or
or its derivatives, such as acrylic acid, methacrylic acid, a-ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, bicyclo[2, 2. 11hept-5-ene-2,3-dicarboxylic acid (nadic acid 7M), methyl-endocys-bicyclo[2, 2. 11 heptose 5-en-2.3
Examples include unsaturated carboxylic acids such as -dicarboxylic acid (methylnadic acid TN), and derivatives of unsaturated dicarboxylic acids such as acid halides, amides, imides, and acid anhydride esters. Specific examples of such derivatives include 6-conversion, 1-conversion malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and dimethyl maleate. These compounds can be used alone or in combination. Among these, maleic acid, nadic acid T
It is preferable to use M or an acid anhydride thereof.

Examples of the styrenic hydrocarbon used here include compounds represented by the following formula.

In the above formula, RIS R2 and R 3 14
Each may be the same or different, and is a hydrogen atom or a lower alkyl group. Specific compounds represented by the above formula include +4 styrene, a-methylstyrene, o,m, or p-monochlorostyrene, olm or p-monomethylstyrene, 0,m or p-monoethylstyrene, 0,m Or p-monoisoprobylstyrene can be mentioned. These can be used alone or in combination. Among these, it is particularly preferable to use styrene, m-methylstyrene or p-methylstyrene in the present invention.

An example of the organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group used herein is a compound represented by the following formula.

RI Re SiYI Y2 RI Consisting of an oxygen atom.Specifically, examples of groups having such an olefinically unsaturated bond include (vinyl, acrylic, pentabutenyl, cyclohexenyl, cyclopentadienyl, and groups represented by the following formulas). be able to.

CH2= C (CHa) COO (CHz)
s-CH2 = C(CH3)Coo(CH2
) 2-0-(C)3-CH2=C CCHs
) COOCHa −〇1CH2 CH (OH) C
Ha O (CH2 ) s - X is an organic group having no olefinic double bond, and may be an alkyl group such as a methyl group, an ethyl group, a proyl penta-tetradecyl group or an octadecyl group, or a phenyl penta-benzyl group or a tolyl group. It is an aryl group.

Furthermore, YI Y2 and Y31t are hydrolyzable groups, and examples of such groups include alkoxy groups such as 1-inverted methoxy, ethoxy, pentabutoxy, methoxyethoxy; alkoxyalkoxy, formyloxy, acyloxy such as acetoxy and propionoxy groups. The residue from which a hydrogen atom has been removed from an oxime as shown below - O N = C ( CH s ) * O N
” C H C H 2 C @ H sON=C
(CsHs)a, and the following alkyl-substituted amino groups or aryl-substituted amino groups; -NHCH3, -NHC2H, and the like. Also Yl, Y2 and Y
3 G-translation Each may be the same or different 8 YIS Compounds in which Y2 and Y3 are the same are particularly preferred. Among these organosilicon compounds, compounds represented by the following formula such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxyethoxy)cyan; RI S iYI Y2 Y3 and vinylmethyldiethoxysilane, vinylphenyldimethoxy Preferably, silane or the like is used.

Examples of the compound used here having at least one polymerizable unsaturated bond and at least one epoxy group in the molecule include compounds represented by the following formula.

Unsaturated glycidyl esters represented by (L and R represent a hydrocarbon group having a polymerizable ethylenically unsaturated bond)
.

Unsaturated glycidyl ethers (just LA R
and R1 have the same meaning as above and represent a divalent group).

Epoxyalkenes represented by (however, R has the same meaning as above and represents a hydrogen atom or a methyl group).

1 circle as a compound each having one polymerizable unsaturated bond and one epoxy group in the molecule as described above.Specifically, glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of itaconic acid,
Mono-, di- and tri-diglycidyl esters of putenttricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endocys-bicyclo[ 2, Z, 11
Mono- and diglycidyl esters of heptose-5-ene-2,3-dicarboxylic acid (nadic acid TI'I), endocys-bicyclo[2.2.1]heptose-5-ene-2
-Methyl-2,3-dicarboxylic acid (methylnadic acid τ
Mono- and diglycidyl esters of I'I), mono- and diglycidyl esters of allylsuccinic acid, mono- and diglycidyl esters of p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3 .4-
Epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,
Examples include 4-epoxy-3-methyl-1-hentene, 5,6-epoxy-1-hexene, and vinylcyclohexane monoxide. These compounds can be used alone or in combination. Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

Known methods can be used to modify (a) or (b) using the modifiers described above. As such, even if! A method for producing a graft copolymer by adding a modifier to the above-mentioned cyclic olefin polymer and melting the copolymer, or dissolving the modifier in a solvent. Examples include a method of mixing and denaturing. In such a method, it is preferable to use a radical initiator in order to efficiently perform graft modification. The radical initiator used here is not particularly limited, and conventional initiators such as organic peroxides, organic peresters, and azo compounds can be used. The reaction can also be carried out by irradiating energy rays such as electron beams or ultraviolet rays with or without using an initiator as described above.

For example, in the modified cyclic olefin random copolymer produced as described above, the amount is usually 50 parts by weight or less, preferably 35 parts by weight or less per 100 parts by weight of the cyclic olefin random copolymer. Modifier is polymerized.

Even when a rod-shaped body made of a modified polymer is formed from a resin with a low modification rate, by performing a specific surface treatment according to the present invention, an excellent rod-shaped body can be obtained. Adhesive properties and paintability can be imparted.

For example, the intrinsic viscosity of a modified cyclic olefin random copolymer measured in decalin at 135°C [7
] is usually 0.03 to 20 dl/preferably 0.0
It is within the range of 5 to 5 dl/g.

The glass transition temperature measured using a dynamic viscometer (DMA) is usually 20-250℃, and even 30℃.
It is in the range of ~220°C, and has excellent heat resistance.

In addition, the softening point of such a modified product is T M A (T
hermo-mechanical analyzer
) with a load of 49g1 and a quartz needle (diameter 0.635
shaft), the quartz needle was heated to 0.5 °C at a heating rate of 5 °C/min.
When measured as the temperature when entering the 1n resin,
The softening point of the above-mentioned modified products is usually in the range of 20 to 230°C, often 30 to 200°C.

Furthermore, the density of the modified cyclic olefin polymer as measured by the method specified in ASTM-D-1505 is usually 0. 95 ~1. 20g/cf,
Preferably 0. 96 to 1.10 g/cm$.

In the present invention, instead of the cyclic olefin random copolymer, the aforementioned ring-opening copolymers or hydrogenated products thereof may be used.

In the present invention, (d) ring-opening polymerization, inter-ring copolymerization imitating hydrogen additive, cyclic olefin random copolymer, or a modified product of these copolymers (cyclic olefin polymer) is further blended with another resin. It is possible to use the composition.

Examples of resins that can be blended into such cyclic olefin polymers include polyolefins such as polyethylene, polypropylene, polymethylbutene-L, poly-4-methylbentene-L, polybutene-L, and polystyrene (these (Polyolefin may have a crosslinked structure.); Halogen-containing vinyl polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, and chlorinated rubber; Polyacrylate, polymethacrylate, polyacrylamide, and Polymers derived from aβ monounsaturated acids such as acrylonitrile or their derivatives; copolymers such as acrylonitrile/butadiene/styrene copolymers, acrylonitrile, styrene/acrylic acid ester copolymers, polyvinyl alcohol, polyvinyl acetate, polystearin Polymers such as vinyl acid, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyacryl phthalate, polyaryl melamine, and monomers constituting the aforementioned polymers such as ethylene-vinyl acetate copolymers and other monomers. Copolymers with epoxy groups such as polyethylene oxide and polymers derived from bisglycidyl ether; Polyacetals such as polyoxymethylene, polyoxyethylene, and polyoxymethylene containing ethylene oxide as a comonomer; Polyphenylene oxide: polycarbonates; polysulfonate polyurethanes and urea resins; polyamides or copolyamides such as nylon 6, nylon 66, nylon 11 and nylon 12; polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate and polyethylene naphthalate I Polyesters such as phenols, formaldehyde resins, urea/formaldehyde resins, and polymers with crosslinked structures such as melamine/formaldehyde resins; alkyd resins such as glycerin/phthalic acid resins; Unsaturated polyester resins derived from polyesters and crosslinked with vinyl compounds, and resins in which at least some of the hydrogen atoms present in these resins are replaced with halogen atoms; cellulose acetate, cellulose probionate, cellulose esters, etc. Cellulose rubber, protein, or derivatives thereof; a-olefin copolymers, a-olefin/diene copolymers, aromatic vinyl hydrocarbon/conjugated diene soft copolymers, and imbutylene or isobutylene as shown below; - Soft polymers consisting of conjugated genes can be mentioned.

The a-olefin copolymer used here is a non-quality or low-crystalline copolymer consisting of at least two types of a-olefins. A specific example is a copolymer of IL ethylene and an a-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, in which the ethylene fractional unit and the a-olefin fractional unit are The molar ratio is preferably within the range of 1440:60 to 95:5.

In addition, when the a-olefin is propylene, the above ratio is preferably in the range of 40:60 to 90:10, and when the a-olefin is an olefin having 4 or more carbon atoms, the above ratio is preferably in the range of 40:60 to 90:10. Ratio 1 gourd 50:50-95:5
It is preferable that it is within the range of . In addition, as an a-refined copolymer, propylene and carbon atoms of 4 to 20
A copolymer formed from a-olefin and an a-olefin can be used, in which case the molar ratio of propylene fractional units and a-olefin fractional units is 50:50 to 95;
It is preferably within the range of 5.

As the a-olefin/diene copolymer used for the soft polymer, specifically, ethylene/a-olefin/diene copolymer rubber and propylene/q-olefin diene copolymer rubber are used. The diene components used here are 141.4-hexadiene, 1.6-octadiene, 2-methyl-1.5-hexadiene, 6-
Methyl-1,5-hebutadiene, 7-methyl-1,6-
Chain nonconjugated dienes such as octadiene; cyclohexadiene, dicyclobentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2- norbornene,
Cyclic non-conjugated dienes such as 6-chloromethyl-5-improbenyl-2-norbornene, 2.3-diisopropylidene-5-norbornene, 2-ethylidene-3-impropylidene-5-norbornene, 2-propenyl-2 Dienes such as .2-norbornene can be mentioned. In addition, when a plurality of α-olefins are used, the molar ratio of each olefin is the same as in the case of the α-olefin copolymer, and a certain content of diene in this copolymer (4 is 1-2
0 mol%, preferably 2 to 15 mol%.

Aromatic vinyl hydrocarbon/conjugated diene soft copolymers used in soft polymers include a wide variety of random copolymers of aromatic vinyl hydrocarbons and conjugated dienes.
Block copolymers or hydrides thereof may be mentioned. Specific examples of aromatic vinyl hydrocarbon/conjugated diene soft copolymers include styrene/butadiene block copolymer rubber, styrene/butadiene block copolymer rubber, and styrene/butadiene block copolymer rubber.
Styrene block copolymer rubber, styrene/isoprene block copolymer rubber, styrene/isoprene/styrene block copolymer rubber, hydrogenated styrene/butadiene; Styrene block copolymer rubber, styrene/butadiene random copolymer rubber. be able to. In these copolymer rubbers, the molar ratio of aromatic vinyl hydrocarbon to conjugated diene is usually 10:90 to 70:
It is within the range of 30. In addition, the above copolymer rubber tag
Hydrogenated copolymer rubber and 1-turn This is a copolymer rubber in which some or all of the load bonds remaining in the above copolymer rubber are hydrogenated.

Specific examples of the soft polymer made of isobutylene or isobutylene/conjugated diene used in the soft polymer include: -converted polyisobutylene rubber, polyisoprene rubber, polybutadiene rubber/isoprene copolymer rubber, and the like.

The above-mentioned soft polymer has an intrinsic viscosity [η] measured in decalin at 135°C, which is usually 1 to 0.01 to 10 dl/
Preferably within the range of 0.08 to 7 dl/g,
Glass transition temperature is usually below 0°C, preferably -20°C
The degree of crystallinity measured by X-ray diffraction is usually in the range of o-io%, preferably in the range of O to 7%, particularly preferably in the range of 0 to 5%.

Resins other than such cyclic olefin polymers or modified products thereof (9) Used in an amount of 150 parts by weight or less, preferably 100 to 5 parts by weight, per 10 parts by weight of cyclic olefin polymers or modified products thereof. .

Blending other resins into the above-mentioned cyclic olefin polymers 14 It can be produced by mixing (or cross-mixing) the cyclic olefin polymers and other resins according to the usual method, and usually, By manufacturing as described above, a polymer alloy containing a cyclic olefin/fin type polymer as a main component is produced. That is, in the above polymer alloy, other resins are finely dispersed in the monocyclic olefin polymer, and this polymer alloy has excellent properties.

Such polymer alloys can also be used after being crosslinked. Such crosslinking is particularly effective when the other resin contains some rubber, especially the above-mentioned soft copolymer.

Such a crosslinked polymer alloy can be produced, for example, as follows.

The above-mentioned cyclic olefin polymer and the rubber, especially the above-mentioned soft copolymer, are added to 5 to 150 weight parts of paper, preferably 5 to 100 weight parts of paper, more preferably 5 to 100 weight parts of the cyclic olefin polymer. 10 to 80 parts by weight of mixed fox then kneaded. The melt flow index (MFR; ASTM D1238 conditions) of such polymer alloys is usually 0. It is 1-100.

14 for crosslinking polymer alloys such as those described above.
Usually organic peroxides are used.

Examples of organic peroxides that can be used in the present invention include ketooxides such as methyl ethyl ketoperoxide and cyclohexanone peroxide: 1,1-bis(t-butylperoxy)cyclohexane and 2,2-bis(
Peroxy ketals such as t-butylhydroberoxide) octane; t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide and 1. 1. 3. Hydroperoxides such as 3-tetramethylbutyl hydroperoxide; di-t-butyl peroxide, 2,5-dimethyl-2.
5-di(t-butylbaroxy)hexane and 2,5
-Dialkyl peroxides such as dimethyl-2,5-di(t-butyl baroxy)hexyne-3; Diasilver oxides such as lauroyl peroxide and benzoyl peroxide; t-butyl baroxy acetate, t-butyl bar oxide Oxybenzoate, 2.
Examples include peroxy esters such as 5-dimethyl-2,5-di(benzoylbaroxy)hexane.

Amount 13 of the above organic peroxide: Usually 0.01-1 weight part of paper, preferably 0.05-0, per 100 parts by weight of the total weight of the cyclic olefin polymer and other resins.
．． 5 parts by weight.

Further, by incorporating a compound having two or more radically polymerizable functional groups in the molecule during treatment with an organic peroxide, the properties such as impact resistance of the obtained polymer alloy are improved.

Examples of compounds having two or more functional groups in the molecule used in this way include IL divinylbenzene, (
Examples include vinyl meth)acrylate. These compounds are usually used in an amount of 1 part by weight or less, preferably O. It is used in amounts ranging from 1 to 0.5 parts by weight.

In the present invention, the resin molded article to be surface-treated may be a ring-opening copolymer or a hydrogenated cyclic olefin random copolymer or a modified product thereof as described above. The composition is formed from at least one resin out of a composition of a cyclic olefin polymer and another resin.

(Hereinafter, blank spaces) In the present invention, additives may be further blended into the above-mentioned resin if desired.

Examples of additives that can be used in the present invention include: heat-resistant stabilization L, souko-stabilization, anti-static cooling L, slip life L, anti-blocking agent L, anti-ikK, slip rope, dyes, pigments, natural ponds, wax, Organic fillers and inorganic fillers can be mentioned.

Examples of substances that can improve the stability of the cyclic olefin resin used in the present invention include tetrakis[methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate]methane, β -(3.5-
Phenolic antioxidants such as di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2.2°-oxamidobisethyl-3-(3.3-di-t-butyl-4-hydroxyphenyl)probionate; stearin acid zinc, calcium stearate, 1.2-
Examples include fatty acid metal salts such as calcium hydroxystearate, polyhydric alcohol fatty acid esters such as glycerin distearate, bentaerythritol monostearate, pentaerythritol distearate, and bentaerythritol tristearate. These can be used alone or in combination.

An example of such a combination is a combination of tetrakis[methylene-3-(3.5-di-t-butyl-4-hydroxyphenyl)propionate]methane, zinc stearate, and glycerin monostearate.

In addition, as inorganic fillers that can be used in the present invention, specific examples of inorganic fillers include (transformed silica, diatomaceous earth, titanium oxide,
Magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay
Examples include mica, asbestos, glass flakes, glass beads, calcium silicate, montmolystite, bentonite, graphite, aluminum powder, molybdenum sulfate, boron fibers, and silicon carbide fibers. Examples of organic fillers include polyethylene fibers, polypropylene fibers, polyester fibers, polyamide fibers, and polyimide fibers. These can be used alone or in combination,
These can be blended in amounts within normal ranges. Further, there is no particular restriction on the method of blending these, and for example, they can be blended into the resin by kneading the cyclic olefin resin.

In the present invention, the cyclic olefin resin prepared as described above is used to produce a cylindrical body.

The rod-shaped body can be manufactured by employing known methods such as injection molding, blow molding, extrusion molding, and flowing method. Therefore, there is no particular restriction on the shape of the precept used in the present invention, and it can be shaped to correspond to a desired container shape or component material, and can also be shaped into a film or sheet.

The surface to be bonded or the surface to be painted of the resin molded body obtained as described above is brought into contact with plasma.

In order to bring the surface of the resin shaped body into contact with plasma, the surface of the resin shaped body may be subjected to plasma discharge treatment, glow discharge treatment, or corona discharge treatment, for example.

Furthermore, in the present invention, a plasma jet treatment or the like can be used in which high-temperature plasma is generated using arc discharge or the like and the plasma is brought into contact with the surface of the preform. Furthermore, although the generated plasma is usually brought into direct contact with the surface of the compact, for example, L
The plasma may be brought into contact with the surface of the molded body through a window such as iF.

In the present invention, plasma treatment is performed by, for example, placing the molded article manufactured as described above in a plasma treatment apparatus,
The air in the device is replaced with argon, nitrogen, or a mixed gas of nitrogen and oxygen, and then the degree of vacuum in the device is adjusted to usually 0.1 to 10 torr, preferably 0.2 to 5 to 5 torr, and then the voltage is is applied to generate plasma, and this plasma is made to collide with the surface of the rod-shaped body.

In the present invention, output 1 during plasma processing as described above
4 Usually 100-IOOOOW1 Preferably 50
Please adjust within the range of 0 to IOOOW.
It is preferable to process while applying a high frequency of KHz to 2450 MHz.

The plasma processing time as described above is usually i.
o to 300 seconds, preferably 30 to 60 seconds.

Further, by generating a corona discharge between the precept-shaped body to be treated and the electrode, a treatment similar to the above-mentioned plasma treatment can be performed.

Even if the surface of the cyclic olefin random copolymer is subjected to plasma treatment or corona treatment and brought into contact with plasma in this manner, the excellent properties of the cyclic olefin random copolymer are not impaired.

By performing the plasma treatment or corona treatment as described above, it is assumed that the surface of the cylindrical body is modified and polar groups are mainly formed on the surface. Since only the treated surface area of the molded body and only a small portion of the whole body is modified, the characteristics of the body itself do not change.

The effects of the polar groups exerted by this treatment or the physical changes in the surface condition of the molded body work together to significantly improve the adhesion and paintability of the molded body.

Therefore, various adhesives can be used to adhere other resins to the treated surface of the shaped body treated as described above.

14 as an adhesive that can be used in this case
Acrylic adhesive Y$L Urethane adhesive Longevity Epoxy adhesive L Cyanoacrylate adhesive L Amino resin adhesive＊l Vinyl acetate resin emulsion adhesive Phenol resin adhesive L Vinyl acetate adhesive Maleic anhydride modified Mention may be made of olefin adhesives, EVA emulsion adhesives and Hewei rubber adhesives. In addition to the above-mentioned reaction-curing adhesive, a solvent-diluted adhesive such as one containing vinyl acetate resin as its main ingredient may also be used as the adhesive.

The resins that can be bonded to the treated surface of the molded body using the above adhesive include polyvinyl chloride resin, polyester resin, polycarbonate resin, polyamide resin, polyacetal resin, polyphenylene oxide resin, polystyrene resin, and acrylonitrile/styrene resin.・AB
S resin, polyethylene, polypropylene, polyurethane resin, unsaturated polyester resin, epoxy resin, diene rubber, inbutylene rubber, styrene-butadiene rubber, olefin rubber, polyphenylene sulfide resin 1'@S polyimide resin, poly Mention may be made of etheretherketone resins, polysulfones, polyethersulfones, polyamideimides and polyetherimides. There is no particular restriction on the form of the resin to be adhered, and the resin may be adhered in the form of, for example, an injection molded article injected into a desired shape. It can also be used in the form of fibers, etc. It may also be in the form of foam or the like.

In addition, when bonding resins with relatively low adhesive properties such as polyolefins, 1 is also used. It is preferable to perform a treatment such as irradiation treatment, plasma treatment, ion beam treatment, or mechanical treatment before bonding.

In addition, the surface of the precept-shaped object is treated as described above.
Not only does it exhibit excellent adhesion as described above, but it also greatly improves paintability.

There are no particular restrictions on the paint that can be applied to the surface of the rod-shaped object that has been surface-treated as described above. Examples of such paints include 1'1, acrylic paint, urethane paint,
Epoxy paint, oil paint, alkyd resin paint, amino resin paint, unsaturated polyester paint, nitrocertose lacquer vinyl lacquer acrylic lacquer
Mention may be made of polyvinyl acetate emulsion paints and polyacrylate emulsion paints. These paints may be of a type in which a resin and pigment are dispersed in a related solvent, or may be powder paints.

Furthermore, there are no particular restrictions on the method of applying such paint;
Conventionally used methods such as a spray method, an electrostatic electrodeposition method, and a spin coating method can be employed.

The coating thickness of such paint is usually 141 to 200μ.
It is m.

By coating other resins on the surface of the cyclic olefin random copolymer in this way, it is possible to coat the cyclic olefin random copolymer with other resins without impairing the excellent properties of the cyclic olefin random copolymer. In addition to being able to impart excellent properties, arbitrary coloring can be applied to the rod-shaped body.

According to the method of the present invention, the surface of the cyclic olefin-based resin is brought into contact with plasma, which eliminates the adhesion of the cyclic olefin-based resin, which has been an obstacle when using cyclic olefin resin. The paintability and paintability can be improved.

Further, such treatment does not impair the excellent properties of the cyclic olefin resin.

Therefore, by employing the method of the present invention, it is possible to impart excellent properties possessed by other resins to a monomer formed from this copolymer while maintaining the properties of the cyclic olefin resin. The shaped body of the present invention obtained by employing this method has very excellent properties.

Next, the present invention will be explained with reference to examples.
These examples should not be construed as limiting.

First, cyclic olefin random copolymer berene}3.4
Prepare 1 kg of this copolymer, 1 ethylene and 1,
4, 5. 8-dimethano-1. 2, 3, 4,
It is a random copolymer with 4a, 5, 8, 8a-octahydronaphthalene, and the ethylene content in this copolymer is 66 mol%. The intrinsic viscosity [η] of this copolymer is 0. 6 di/glass glass transition temperature is 122°C, MFR2. -C is 15g/min,
The softening temperature is 138°C.

Separately, prepare 0.6 kg of ethylene/propylene random copolymer with an ethylene content of 80 mol%.
The intrinsic viscosity [η] of this copolymer is 2. 2dl/fu
Glass transition temperature is -54°C, MFR, 3. -C is 0.7
g/min.

After thoroughly mixing the above two types of pellets, the cylinder temperature was 2.
The resulting pellets were melt-blended at 20°C and made into pellets using a pelletizer, and injection molding was performed under the following conditions to prepare test pieces of 1 20xl 30x2tw.Injection molding machine cylinder temperature mold temperature injection pressure ■ 4 items Toshiba Machine Is-50PE 250℃ 80℃ Primary/Secondary = 1000/800b/cmt Injection speed Medium speed The test piece obtained as above was plasma treated under the following conditions. Paintability The results are shown in Table 1.

ヱ1 EヱFriends meet ■ Toshiba microwave plasma processing equipment TMW-4 2 1 3 Frequency 2450MHz Output 500W Gas Oa / Na = 1 / 1 hour 30
Vacuum level in seconds / Torr equipment amount'' is 14 degrees.Using air spray on a plasma-treated test piece, urethane paint for automobile exterior panels (Nippon B Chemical El!,
R-271) was coated to a dry film thickness of approximately 35 μm and baked at 100° C. for 30 minutes.

After the obtained test piece was left at room temperature for 2 days, a cross-cut test and an adhesion test were conducted using the following method. Then, a 90 degree peel test was performed by adhering a cross-cut adhesive tape of Scotch 1610 with a width of 2 squares to the cross-cut surface, and the results were expressed as the number of pieces remaining after peeling out of 100 pieces.

(2) Adhesion test Use a cutter blade on the painted surface to a depth of 1 to reach the substrate.
A 180 degree peel test was conducted by forming a strip-shaped cut with a width of 0@1 and pulling the paint film from one end of the test piece with the strip-shaped cut made using a tensile tester. The pulling speed is 50 speeds/min.

(1) Adhesion to soft polyvinyl chloride sheet A soft polyvinyl chloride sheet whose surface had been wiped with methanol in advance and a plasma-treated test piece were bonded together using a urethane adhesive (Sunstar ■).
The bonding conditions were as follows.

Temperature: 120℃, Time: 5 minutes, Load: 0. 3kg/am' As described above, a cutter blade was used to cut the soft polyvinyl chloride sheet adhered to the test piece to a depth of 25 cm to reach the substrate.
A strip-shaped cut with a width of @a is formed.A 180-degree peel test is performed by pulling the paint film from one end of the test piece with this strip-shaped cut made using a tensile tester. The pulling speed is 200 am/min.

(2) Bonding with injection foaming urethane Plasma-treated test piece is set in injection foaming mold
Injected foamed urethane (manufactured by Mitsui Toatsu) was injected and foamed at a foaming ratio of approximately 5 times. After 48 hours, a cutter blade was used to cut the foamed urethane surface into strips of 25@1 width to a depth that reached the substrate. Using a tensile tester, pull the paint film from one end of the test piece with this strip-shaped cut into the shape of 1.
Furthermore, a peel test was performed. The tensile speed is 50. /
It's a minute.

(3) Adhesion with cyclic olefin random copolymer A plasma-treated test piece was cut into a strip shape with a width of 25 cm. Two test pieces as described above were prepared. Plasma-treated surface number λ
12. Epoxy resin (manufactured by Mitsui Petrochemical, Epox AH425X). 5x25. Place the test pieces on top of each other so that the adhesive faces face each other, clip both ends of the test pieces, and cure at 80°C for 40 minutes. The tensile shear adhesive strength was measured at a tensile speed of 50 cm/min.

1 g of Verhexin 25B (manufactured by NOF Ichi) was added to 1 kg of the pellet made of the cyclic olefin random copolymer and the low-crystalline α-olefin copolymer obtained in Example 1. and divinylbenzene at a ratio of 3 g, and thoroughly mixed the shirako mixture using a twin-screw extruder at a cylinder temperature of 230°C.
A pig was treated in the same manner as in Example 1 using the pellets obtained in the form of pellets using a pelletizer.
The coating properties and adhesion were evaluated in the same manner except that a test piece was prepared by plasma treatment and this test piece was used. The results are shown in Table 1.

In Example 1, ethylene and 1, 4, 5. 8-dimethano-
1. 2, 3, 4, 4a, 5, 8, 8a-
It is a random copolymer with octahydronaphthalene (ethylene content: 62 mol%), and has an intrinsic viscosity [η] of 0. 4 7 di/i glass transition point is 137℃, M
Test pieces were prepared in the same manner as above except that a cyclic olefin random copolymer with an ER of 35 g/min and a softening temperature of 148°C was used. Using the obtained plasma-treated test piece, coating properties and adhesion were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1, except that the plasma treatment was not performed. The test piece was evaluated for paintability and adhesion, and the results are shown in Table 1.

Claims (2)

[Claims] (1) Ring-opening polymers or ring-opening copolymers formed by ring-opening polymerization of cyclic olefins represented by the following formula [I], hydrogenated products thereof and modified products thereof, ethylene and the following formula [I]
Copolymers with cyclic olefins represented by [I] and modified products thereof, as well as the ring-opening polymers, ring-opening copolymers, hydrogenated products, copolymers, or modified products of these polymers and other A method for treating a resin molded article, which comprises bringing the surface of a molded article made of at least one type of cyclic olefin resin selected from the group consisting of a composition with a resin into contact with plasma; ▲Mathematical formula, chemical formula, table, etc. There is a Represents an atom or group selected from the group consisting of atoms and hydrocarbon groups, and R^1^5 to R^1^8 may be bonded to each other to form a monocyclic or polycyclic group, and The monocyclic or polycyclic group may have a double bond, and R^1^5 and R^1^6, or R^1^7
and R^1^8 may form an alkylidene group). (2) Ring-opening polymers or ring-opening copolymers obtained by ring-opening polymerization of cyclic olefins represented by the following formula [I], hydrogenated products thereof and modified products thereof, ethylene and the following formula [
Copolymers with cyclic olefins represented by I], modified products thereof, and combinations of the ring-opening polymers, ring-opening copolymers, hydrogenated products, copolymers, or modified products thereof with other resins. A resin molded article characterized in that the surface of the molded article made of at least one type of cyclic olefin resin selected from the group consisting of compositions is plasma-treated; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...・[I] (In the formula, n is 0 or 1, m is 0 or a positive integer, and each of R^1 to R^1^8 independently consists of a hydrogen atom, a halogen atom, and a hydrocarbon group) Represents an atom or group selected from the group, R^1^5 to R^1^8 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group The group may have a double bond, and R^1^5 and R^1^8 or R^1^7
and R^1^8 may form an alkylidene group).