JPH10273564A - Cycloolefin resin molding and method for printing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molding having excellent transparency, heat resistance, moistureproofness, chemical resistance, solvent resistance, processability, electrical properties, mechanical in properties, low birefingency, etc., and being excellent printing characteristics in especially laser printing by bringing a cycloolefin resin molding into contact with gaseous or liquid carbon dioxide. SOLUTION: The cycloolefin resin used is a random copolymer of ethylene with a cycloolefin of formula I (wherein n is 0 or 1; m is 0 or a positive integer; q is 0 or 1; R<1> to R<18> , R<a> and R<b> are each H, a halogen, a (halogen-substituted) hydrocarbon (R<15> to R<18> may be suitably combined with each other to form a mono- or poly-cyclic ring); or the like) or of formula II (wherein p and q are each 0 or a positive integer; m and n are each 0-2; R<1> to R<19> are each H, a halogen, a (halogen-substituted) hydrocarbon or an alkoxyl; etc.), a ring- opening (co)polymer of cycloolefins of formula I or II or a product of hydrogenation of a ring-opening (co)polymer of a cycloolefin of formula I or II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention is excellent in transparency, heat resistance, moisture resistance, chemical resistance, solvent resistance, moldability, electrical properties, mechanical strength, low birefringence, etc. The present invention relates to a molded article of a cyclic olefin-based resin having excellent printing characteristics when used for printing and a method for printing the molded article.

[0002]

BACKGROUND OF THE INVENTION Conventional polyolefins are known as resins having excellent mechanical properties and chemical resistance.
Transparency was not necessarily sufficient except for some such as poly-4-methyl-1-pentene. On the other hand, as a polyolefin having a good balance between rigidity and transparency, a cyclic olefin-based resin derived from a bulky cyclic olefin has been proposed. For example, as a random copolymer of this bulky cyclic olefin and ethylene, ethylene and 2,3-
A copolymer with dihydroxydicyclopentadiene (US Pat. No. 2,883,372) or a copolymer of ethylene and 5-ethylidene norbornene has been proposed.

[0003] The present applicant has also studied such a cyclic olefin-based resin. In particular, amorphous cyclic olefin-based resins such as a copolymer of ethylene and a cyclic olefin have been converted to α-olefin (co) polymers. Compared with various properties, such as transparency, low birefringence, moisture resistance (low water absorption), heat resistance, chemical resistance, solvent resistance, precision molding processability, dielectric properties, etc. , And have excellent mechanical properties and rigidity.

[0004] For this reason, cyclic olefin-based resins can be used for a wide variety of applications. In particular, their excellent transparency is effectively used for optical applications, medical / pharmaceutical containers, food containers and the like. The use of is considered.

[0005] Among these uses, particularly when a molded article made of a cyclic olefin resin is used for various containers, it is common to print the name and quality of the contents on the surface of the container.

The printing method includes an impact printing method in which printing is performed by mechanically hitting an object to be printed, and a printing method without mechanically hitting an object to be printed, such as an ink jet printing apparatus. And a non-impact printing method. In these methods, it is pointed out that even if the apparatus is inexpensive, the cost of consumables is high, labor is difficult due to the need for maintenance, and problems related to the working environment due to the use of ink solvents during printing are pointed out. ing.

In recent years, there has been an increasing demand for more reliable printing. In particular, in the case of an impact printing method, distortion, variation, chipping, etc. of characters due to printing pressure may occur. Was difficult.

For this reason, attention has been paid to printing by a laser marking method, which is a non-impact printing method that does not use an ink solvent and does not need to consider the printing pressure. In this laser marking method, marking or printing is performed by melting or carbonizing the surface of an object to be printed, for example, a resin. Therefore, the printing durability is good because the ink does not peel off after printing unlike the ink solvent, and a large-scale line such as printing is not required. It has the advantage of being low.

However, even if an attempt is made to print on a cyclic olefin resin molded article by a usual laser marking method,
Clear characters cannot be obtained. This is because the resin itself has high transparency and transmits laser light, so that melting or carbonization of the resin surface does not easily occur. Therefore,
By increasing the output of laser light, the resin surface melts,
Alternatively, a method of engraving or printing by carbonization can be considered, but it is difficult to perform clear printing also by this method.

Therefore, the present inventor has studied a method for printing on the surface of a cyclic olefin resin molded article using a laser. As a result, the cyclic olefin resin absorbs carbon dioxide gas easily, and the resin that once absorbs carbon dioxide gas easily foams by heating. By irradiating the surface of the molded article made of the resin with laser light, it was found that printing with good contrast was obtained, and the present invention was completed.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has transparency, heat resistance, moisture resistance, chemical resistance, solvent resistance, moldability, electrical properties, mechanical strength, It is an object of the present invention to provide a cyclic olefin resin molded article having excellent low birefringence and the like and capable of being printed by using a laser, and a printing method for printing clear characters on the surface of the molded article. It is intended to provide.

[0012]

SUMMARY OF THE INVENTION A cyclic olefin resin molded article according to the present invention comprises a molded article formed of a cyclic olefin resin,
It is obtained by contact treatment with gaseous or liquid carbon dioxide.

In the present invention, the above treatment is preferably performed in a gaseous carbon dioxide (ie, carbon dioxide gas) atmosphere. The cyclic olefin-based resin is (1) the following [A-
1], [A-2] and [A-3], and (2) softening point temperature (T
MA) is 70 ° C. or higher, and (3) the melt flow rate (MFR: measured at 260 ° C., 2160 g) is:
[A-1] a random copolymer of ethylene and a cyclic olefin represented by the following formula [I] or [II];

[0014]

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(In the formula [I], n is 0 or 1, m
Is 0 or a positive integer; q is 0 or 1;
^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group optionally substituted with halogen, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. And the monocyclic or polycyclic ring may have a double bond, and may form an alkylidene group with R ¹⁵ and R ¹⁶ or with R ¹⁷ and R ^18. You may. ),

[0016]

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(In the formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group which may be substituted with halogen, and a carbon atom to which R ⁹ or R ¹⁰ is bonded and R ¹³ are bonded to each other. May be directly or via an alkylene group having 1 to 3 carbon atoms, or may be bonded to the carbon atom to which R ¹¹ is bonded. When n = m = 0, R ¹⁵ and R ¹² or R ^{12 15} and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ), [A-
2] A ring-opened polymer or copolymer of the cyclic olefin represented by the formula [I] or [II], and [A-3] a hydride of the ring-opened polymer or copolymer [A-2].

In the method for printing a molded article according to the present invention, the above-mentioned cyclic olefin resin molded article is subjected to a contact treatment with gaseous or liquid carbon dioxide, and then, the molded article is printed using a laser. It is characterized by.

Further, as the above laser, it is preferable that the laser source is a carbon dioxide laser.

[0020]

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin resin molded article according to the present invention and a method for printing the molded article will be described below.

Cyclic olefin resin molded article The cyclic olefin resin molded article according to the present invention is obtained by subjecting a molded article formed of a cyclic olefin resin to contact treatment with gaseous or liquid carbon dioxide. And

This cyclic olefin resin molded article can be obtained by molding a cyclic olefin resin described below into a desired shape by a known molding method. For example, a cyclic olefin resin is formed into a lens, a container, a tray, a sheet, or a film by a molding method such as an injection molding method, an injection blow molding method, a direct blow molding method, a T-die extrusion method, an inflation method, and a pressing method. It is obtained by molding into a shape.

Here, the cyclic olefin resin used in the present invention will be described. In the present invention, [A-1] ethylene and the following formula [I] or [I
I] a random copolymer with a cyclic olefin represented by the formula:
[A-2] a ring-opened polymer or copolymer of a cyclic olefin represented by the following formula [I] or [II], or [A-3] a ring-opened polymer or copolymer of the above [A-2] Hydrides are used.

The cyclic olefin resin [A-
The cyclic olefin represented by the formula [I] or [II] that forms [1] to [A-3] will be described. Cyclic olefin

[0025]

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In the above formula [I], n is 0 or 1,
m is 0 or a positive integer, and q is 0 or 1.
When q is 1, R ^a and R ^b are each independently the following atoms or hydrocarbon groups. When q is 0, each bond is bonded to form a 5-membered ring. Form.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the hydrocarbon group independently include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. A cyclohexyl group is mentioned, and a phenyl group, a naphthyl group, etc. are mentioned as an aromatic hydrocarbon group.

These hydrocarbon groups may be substituted with a halogen atom. Further, in the above formula [I], R
^{15 to} R ¹⁸ may be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. Is also good. Specific examples of the monocyclic or polycyclic rings formed here are shown below.

[0030]

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In the above examples, carbon atoms numbered 1 or 2 are each represented by R ¹⁵ in the formula [I].
The carbon atom to which (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is attached is shown.

Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0033]

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In the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

The halogen atom has the same meaning as the halogen atom in the above formula [I]. Further, as the hydrocarbon group, each independently an alkyl group having 1 to 20 carbon atoms,
Examples thereof include a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. More specifically, as the alkyl group,
A methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group; a cycloalkyl group includes a cyclohexyl group; an aromatic hydrocarbon group; Examples thereof include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group.
These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or a carbon atom having 1 to 1 carbon atoms.
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ , or the groups represented by R ¹⁰ and R ^{11 work} together to form a methylene group It forms an alkylene group of any of (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- ).

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. In this case, as the monocyclic or polycyclic aromatic ring, for example, the following n = m = 0
In the above, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0039]

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Here, q has the same meaning as q in the formula [II]. The cyclic olefin represented by the above formula [I] or [II] is more specifically exemplified below.

[0041]

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(In the above formula, the numbers 1 to 7 indicate the position numbers of carbon.) And derivatives obtained by substituting this bicyclo [2.2.1] -2-heptene with a hydrocarbon group. Examples of this hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl,
5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5
-Methyl-5-phenyl, 5-benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl) ,Five-
(Anthracenyl), 5,6-diphenyl and the like.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Bicyclo [2.2.1] such as hexahydroanthracene
2-heptene derivatives and the like.

Tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-
Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives such as methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene; Tricyclo [4.4.0.1
^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1
^2,5 ] -3-undecene and other tricyclo [4.4.0.1 ^2,5 ] -3
-Undecene derivative.

[0045]

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(In the above formula, the numbers 1 to 12 indicate the position numbers of carbon atoms.) And derivatives obtained by substituting them with hydrocarbon groups. Examples of this hydrocarbon group include 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10 -Dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9
-Isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl,
5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-
9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene- 9-
Ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-
Isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-
Dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl),
8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), and 5,6-diphenyl.

Further derivatives include adducts of (cyclopentadiene-acenaphthylene adduct) with cyclopentadiene. Pentacyclo [6.5.1.1
^3,6 .0 ^2,7 .0 ^9,13] -4-pentadecene, and derivatives thereof.

[0048] pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13]
-3-pentadecene, and derivatives thereof. Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4,10- penta octadecadienoic Penta cyclopentadiene octadecadienoic compound such.

[0049] pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13]
-3-hexadecene and its derivatives. Pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene, and derivatives thereof.

[0050] hexacyclo [6.6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0
^9,14] -4-heptadecene and derivatives thereof. Heptacyclo ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3,8 .0 12,16] -5- eicosene, and derivatives thereof.

[0051] heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .0
^3,8 .0 ^12,17] -5-heneicosene, and a derivative thereof.
Octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0
^12,17 ] -5-docosene and derivatives thereof.

[0052] Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1 ^15,18.
0 ^2,10 .0 ^3,8 .0 ^12,21 .0 ^14,19] -5-pentacosene and derivatives thereof. Nonashikuro [10.10.1.1 ^5,8 .1 ^14,21.
1 ^{16, 19} .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^{15, 20]} -6-hexacosenoic,
And its derivatives.

The specific examples of the cyclic olefin represented by the general formula [I] or [II] have been described above. More specific structural examples of these compounds are described in Japanese Patent Application No. 5-1964.
No. 75, paragraph numbers [0032] to [005]
4].

The cyclic olefin resin used in the present invention may contain two or more units derived from the above cyclic olefin. The cyclic olefin represented by the above general formula [I] or [II] can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction.

The cyclic olefin resin used in the present invention is prepared by using the cyclic olefin represented by the formula [I] or [II] as described above, for example, in JP-A-60-168708 and JP-A-60-168708.
1-120816, 61-115912, 61-115916, 61-271
No. 308, No. 61-272216, No. 62-252406 and No. 62-2524
According to a method proposed by the present applicant in a publication such as No. 07, it can be produced by appropriately selecting conditions.

[A-1] Ethylene / cyclic olefin random
Copolymer [A-1] A random copolymer of ethylene and a cyclic olefin generally has a unit derived from ethylene in an amount of 5 to 95 mol%,
The amount of the unit derived from the cyclic olefin is preferably 5 to 95 mol%, preferably 20 to 80 mol%, preferably 20 to 80 mol%.
It is contained in an amount of ~ 80 mol%. The ethylene composition and the cyclic olefin composition can be measured by ¹³ C-NMR.

In this [A-1] ethylene / cyclic olefin random copolymer, the units derived from ethylene and the units derived from the cyclic olefin are randomly arranged and bonded to form a substantially linear unit. It has a like structure. The fact that the copolymer is substantially linear and does not have a substantially gel-like cross-linked structure means that when the copolymer is dissolved in an organic solvent, the solution contains an insoluble component. You can confirm by not having. For example, when the intrinsic viscosity [η] is measured, it can be confirmed by completely dissolving this copolymer in decalin at 135 ° C.

In the [A-1] ethylene / cyclic olefin random copolymer used in the present invention, at least a part of the cyclic olefin represented by the above formula [I] or [II] has the following formula [III] or [III] IV].

[0059]

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In the formula [III], n, m, q, R ¹
R ¹⁸ and R ^a and R ^b have the same meanings as in formula [I].

[0061]

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In the formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the formula [II]. Further, the [A-1] ethylene / cyclic olefin random copolymer as described above has a unit derived from another copolymerizable monomer as needed as long as the object of the present invention is not impaired. It may specifically contain a unit derived from another monomer in an amount of usually 20 mol% or less, preferably 10 mol% or less.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefin. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, Methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-
Α- having 3 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene
Olefin, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano Cycloolefins such as -1H-indene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2 Non-conjugated dienes such as -norbornene.

The ethylene / cyclic olefin random copolymer [A-1] may contain two or more units derived from the above other monomers. Ethylene / cyclic olefin random copolymer [A-1] is obtained by reacting ethylene with formula [I] or [I
It can be produced by using the cyclic olefin represented by the formula [I] according to the production method disclosed in the above publication. Among them, the copolymerization reaction is carried out in a hydrocarbon solvent, and an ethylene / cyclic olefin random copolymer [A-] is used as a catalyst using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent. [1] is preferred.

An ethylene / cyclic olefin random copolymer [A-1] can also be produced using a solid group IV metallocene catalyst. The solid group IV metallocene catalyst is a transition metal compound (metallocene compound) containing a ligand having at least one cyclopentadienyl skeleton.
And an organic aluminum oxy compound and, if necessary, an organic aluminum compound. Here, the group IV transition metal is zirconium, titanium or hafnium. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group which may be substituted with an alkyl group. These groups may be bonded via another group such as an alkylene group. The ligand other than the ligand having a cyclopentadienyl skeleton is usually an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or the like.

As the organic aluminum oxy compound and the organic aluminum compound, those usually used for producing an olefin polymer can be used. Such a solid group IVB metallocene catalyst is described in detail in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112.

[A-2] Ring-opening (co) polymer of cyclic olefin Ring-opening polymer or ring-opening copolymer of cyclic olefin [A-2]
In the formula, at least a part of the unit derived from the cyclic olefin represented by the formula [I] or [II] is considered to be represented by the following formula [V] or [VI].

[0068]

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In the formula [V], n, m, q and R ¹
To R ¹⁸ and R ^a and R ^b have the same meanings as in formula [I].

[0070]

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In the formula [VI], n, m, p, q and R ^{1 to} R ¹⁹ have the same meaning as in the formula [II]. Such a ring-opened (co) polymer can be produced by the production method disclosed in the above-mentioned gazette. For example, a cyclic olefin represented by the above formula [I] is polymerized or polymerized in the presence of a ring-opening polymerization catalyst. It can be produced by copolymerization.

Examples of such a ring-opening polymerization catalyst include a catalyst comprising a halide, nitrate or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, indium or platinum, and a reducing agent; A catalyst comprising a halide or acetylacetone compound of a metal selected from palladium, zirconium or molybdenum and an organoaluminum compound can be used.

[A-3] A hydride of a ring-opening (co) polymer A hydride of a ring-opening (co) polymer [A-3] is a ring-opening polymer or a ring-opening copolymer as described above [ A-2] in the presence of a conventionally known hydrogenation catalyst.

In the ring-opened (co) polymer hydride [A-3], at least a part of the unit derived from the formula [I] or [II] is represented by the following formula [VII] or [VIII]. It is considered to be.

[0075]

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In the formula [VII], n, m, q and R
^{1 to} R ¹⁸ and ^Ra and ^Rb have the same meaning as in formula [I].

[0077]

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In the formula [VIII], n, m, p, q, R
^{1 to} R ¹⁹ have the same meaning as in formula [II]. In the present invention, the above-mentioned [A-1] and [A-2]
And [A-3] may be used alone, two or more of the same may be used, or a combination of these may be used.

Of these, an ethylene / cyclic olefin random copolymer [A-1] is preferably used as the cyclic olefin resin. The crystallinity of the cyclic olefin-based resin measured by the X-ray diffraction method is 0 to 20.
%, Preferably 0 to 2%.

The softening point (TMA) of the cyclic olefin resin used in the present invention is 70 ° C. or higher, preferably 80 to 250 ° C., more preferably 90 to 200 ° C.
It is. The glass transition temperature (Tg) is desirably 60 ° C or higher, preferably 70 to 240 ° C.

The MFR (26)
0 ° C., 2160 g) is 0.1 to 100,
Preferably, it is 1 to 80. The intrinsic viscosity [η] (in decalin at 135 ° C.) of the cyclic olefin-based resin is 0.05 to 10 dl / g, and preferably 0.08 to 5 dl / g.

The cyclic olefin resin used in the present invention may further include a conventionally known heat stabilizer, weather stabilizer, antistatic agent, slip agent, antiblocking agent, antifogging agent, lubricant, dye, pigment, natural Oil, synthetic oil, wax, mica, talc, glass fiber, barium sulfate and the like may be blended.

Carbon dioxide contact treatment conditions The cyclic olefin resin molded article according to the present invention is obtained by subjecting a molded article obtained by molding the above cyclic olefin resin to contact treatment with gaseous or liquid carbon dioxide. can get.

When the cyclic olefin resin molded article is contacted with gaseous carbon dioxide, the carbon dioxide gas pressure is as follows:
The pressure is 0.5 to 50 atm, preferably 1 to 20 atm. The contact treatment temperature is not limited as long as the molded body is not deformed, but is generally -10 to 100C, preferably 0 to 100C.
~ 50 ° C is preferred. The contact treatment time varies depending on the treatment pressure and the treatment temperature, but is 1 minute to 7 days, preferably 1 hour to 3 days.

Further, when a composition obtained by adding mica to the above-mentioned cyclic olefin-based resin is molded and the molded product is treated with carbon dioxide as described above, a clearer character can be obtained by a printing method described later. It is preferable because a molded body that can obtain the following is obtained.

The mica has the general formula A (B, C) _2-3 D ₄ O ₁₀ (OH, O) ₂ (where A is K, Na, Ca, Li;
C) is Fe ^II , Fe ^III , Mn, Al, Mg, V; D is Si, Al).

The mica of the above formula can be divided into the following two groups: 1) White moth series (K, Na, Li) (Al, Mg,
V) ₂ (Si, Al) ₄ O ₁₀ (OH) ₂ , for example, brown moth, red moth, sodown moly, sericite, vanadin moor, illite, etc .; 2) black moum series K (Mg, Fe ^II , Al) ₃ (S
i, Al) ₄ O ₁₀ (OH, O) ₂ , for example,
Kinunmo, Tetsuunmo, Chinwaldunmo etc.

In addition to these, other plum minerals such as, for example, karyokuite and celadonite are also included. The average particle size of the mica is usually 200 μm or less, preferably 0.1 to 100 μm, particularly preferably 0.1 to 50 μm.
It is.

This mica is made of a cyclic olefin resin 10
It is contained in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 0 parts by weight. In general, when the content of mica is increased, the transparency of the resin is reduced. Therefore, particularly in applications where the transparency of the molded article is required, the range of 0.1 to 1 part by weight is preferable.

As described above, by subjecting the cyclic olefin-based resin molded body to contact treatment with gaseous or liquid carbon dioxide, for example, when the surface of the molded body is locally heated by laser light irradiation, the surface of the molded body is foamed. Thus, clear printing can be performed. Further, when the printing conditions are adjusted by adjusting the intensity of the irradiation laser beam, the contrast of the printing can be increased by melting or carbonizing the printing portion.

Method for Printing Cyclic Olefin-Based Resin Molded Article The method for printing a cyclic olefin-based resin molded article of the present invention comprises:
The cyclic olefin resin molded body subjected to the carbon dioxide treatment is printed using a laser.

In the present invention, "printing" includes, as described above, not only characters representing the name and quality of the contents, but also various symbols, figures, designs, patterns, etc. other than characters. It is a concept.

Here, a laser marking method is employed as a method of printing using a laser, and the type of laser used in this laser marking method may be any of general processing lasers, and particularly, a wavelength of 1064.
ND: YAG (neodymium:
Yttrium - aluminum - garnet) laser, CO ₂ laser for generating an infrared ray having a wavelength of 10.6 [mu] m, such as an excimer laser and the like for generating a pulsed laser in the ultraviolet range of wavelengths 193～351Nm.

The laser marking method specifically includes a scanning marking method and a mask marking method. These methods are selected depending on conditions such as the material of the molded article to be marked, the size of the mark to be obtained, the printing speed, and the like.

In the scanning marking method, two rotating mirrors and a condensing lens are arranged on the optical axis of light emitted from a laser oscillator, and the operation of these rotating mirrors is controlled so that the emitted light is printed. This is a method of two-dimensionally controlling the position reaching the object and printing accurately, and is particularly adopted when marking is performed with an arbitrary typeface.

In the mask marking method, a mask (stencil) serving as a mark for printing and a condenser lens are arranged on the optical axis of the light emitted from the laser oscillator. This is a method of printing a mark when it arrives, and is adopted when high-speed printing and printing of very small letters are required.

In either method, printing is performed by absorbing the energy of the laser beam reaching the object to be printed, ie, the surface of the molded body, and forming a foam bubble to change the light transmittance. Further, depending on printing conditions such as the output of laser light, marking can be performed by melting the surface of the molded body, and only the portion irradiated with the laser light can be carbonized. The engraving or carbonization improves the contrast of the printed characters.

According to the laser marking method, the working environment at the time of printing is improved because no solvent is used, and since it is a non-impact type printing method, there is no occurrence of distortion, variation, chipping, etc. of characters due to printing pressure. Since it does not peel off after printing like ink, it has improved character durability and is suitable for applications requiring reliable and reliable medicine containers and the like. There is an advantage that running costs are low because special auxiliary materials are not required.

When printing is performed by the laser marking method using the cyclic olefin resin molded article of the present invention,
Clear characters can be printed on the surface of the molded article.

[0100]

According to the present invention, excellent transparency, heat resistance, moisture resistance, chemical resistance, solvent resistance, moldability, electrical properties, mechanical strength, low birefringence, etc. It is possible to provide a cyclic olefin-based resin molded article that can be printed by using the resin.

In addition, clear characters can be printed on the surface of the above-mentioned cyclic olefin resin molded product, and when printing on such a molded product surface, the working environment for printing is improved, and distortion and variation of characters are improved. It is possible to provide a printing method in which chipping does not occur, character durability is improved, and running cost is low.

[0102]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

In Examples and Comparative Examples, printing was performed on the surface of the obtained molded body, and the printing quality such as sharpness was visually judged.

[0104]

Example 1 An ethylene / norbornene copolymer formed from ethylene and norbornene as a cyclic olefin resin [TMA: 90 ° C., glass transition point: 80]
° C, MFR (measured at 260 ° C, 2160 g): 3
0 g / 10 min] to form a square plate by ordinary injection molding.

This square plate was placed in a pressure-resistant container, and carbon dioxide gas was introduced to adjust the pressure to 10 atm. After standing at 23 ° C. for 24 hours in this state, it was taken out and printed using a carbon dioxide laser. Table 1 shows the results.

[0106]

Example 2 100 parts by weight of the ethylene-norbornene copolymer produced in Example 1 was mixed with mica (manufactured by Merck Co., Ltd.).
(Iriodin LS-800) 0.2 part by weight was blended and melt-kneaded with a twin-screw extruder. Using the obtained pellets, a square plate was formed by an injection molding machine. This square plate was subjected to carbon dioxide gas treatment under the same conditions as in Example 1, and printing was performed using a carbon dioxide gas laser. Table 1 shows the results.

[0107]

Example 3 Instead of the ethylene-norbornene copolymer used in Example 1, an ethylene-tetracyclododecene copolymer [TMA: 90 ° C., glass transition point measured by DSC: 140 ° C., MFR (260 (Measured under the conditions of 2160 g) and 10 g / 10 min], and printing was performed on the obtained square plate in the same manner as in Example 1. Table 1 shows the results.

[0108]

Comparative Example 1 A square plate was formed by injection molding using the ethylene / tetracyclododecene copolymer used in Example 3, and the square plate was subjected to a carbon dioxide gas laser without carbon dioxide treatment. Printing was performed. Table 1 shows the results.

[0109]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 65/00 B41M 5/26 S

Claims (4)

[Claims] 1. A cyclic olefin resin molded article obtained by subjecting a molded article formed of a cyclic olefin resin to contact treatment with gaseous or liquid carbon dioxide. 2. The cyclic olefin resin according to claim 1, wherein (1)
[A-1], [A-2] and [A-3], (2) a softening point temperature (TMA) of 70 ° C. or more, and (3) a melt flow rate (MFR: 260 ° C., (Measured under conditions of 2160 g)
Is 0.1 to 100 g / 10 min, [A-1] ethylene and a cyclic olefin represented by the following formula [I] or [II]. A random copolymer with: (In the formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently hydrogen. An atom, a halogen atom or a hydrocarbon group optionally substituted by halogen, wherein R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring; It may have a double bond, and R ¹⁵ and R ¹⁶ or R ^15
17 and R ¹⁸ may form an alkylidene group. ), Embedded image (In the formula [II], p and q are 0 or a positive integer,
m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group optionally substituted by halogen,
The carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ), [A-2] a ring-opening polymer or copolymer of a cyclic olefin represented by the above formula [I] or [II], and [A-3] a ring-opening polymer or copolymer [A-2] ] Hydride. 3. A method for printing a molded article, comprising: subjecting a molded article formed from a cyclic olefin resin to contact treatment with gaseous or liquid carbon dioxide, and then printing the molded article using a laser. . 4. The method according to claim 3, wherein the laser source is a carbon dioxide gas laser.