WO2007132641A1

WO2007132641A1 - Cycloolefinic resin composition

Info

Publication number: WO2007132641A1
Application number: PCT/JP2007/058731
Authority: WO
Inventors: Haruo Ichikawa; Katsuhiko Sumita; Hajime Serizawa; Hiroyuki Kanai
Original assignee: Daicel Chemical Industries, Ltd.
Priority date: 2006-05-12
Filing date: 2007-04-23
Publication date: 2007-11-22
Also published as: JPWO2007132641A1

Abstract

A cycloolefinic resin composition which exhibits excellent transparency and surface appearance even when molded into film or sheeting. The composition comprises as the polymer components a cycloolefinic resin (A1) and a low-molecular cycloolefinic resin (A2) having a number-average molecular weight of 10000 or below. The cycloolefinic resin (A1) and the low-molecular cycloolefinic resin (A2) may be each a copolymer of a polycyclic olefin and a linear olefin. The number-average molecular weight of the cycloolefinic resin (A1) may be about 15000 to 200000, while that of the low-molecular cycloolefinic resin (A2) may be about 500 to 8000. The content of the resin (A2) is about 0.1 to 50 parts by weight per 100 parts by weight of the resin (A1).

Description

Specification

Cyclic olefin resin composition

Technical field

The present invention relates to a cyclic olefin-based resin composition excellent in appearance characteristics such as surface smoothness and a molded article thereof.

Background art

[0002] Cyclic olefin-based resins are used as materials for optical applications, medicines or medical devices, etc. because they are excellent in transparency, chemical resistance, moisture resistance, mechanical properties and the like. For example, depending on various molding methods such as injection molding, blow molding, and extrusion molding, optical parts such as lenses and optical recording materials, electric or electronic parts such as connectors and capacitors, medicines or medicals such as medicine containers and syringes. Equipment supplies and laboratory tools such as beakers and optical cells are molded. The cyclic olefin-based resin is also excellent in melt processability and fluidity, and is also used for film-like or sheet-like molded articles, and packaging materials such as blister packages. Furthermore, cyclic olefin-based resins are also used as shrink films (for example, shrink caps, sleeves of bottles, batteries, etc.) because they are excellent in heat shrinkability and printing characteristics.

For example, in JP-A-5-32833 (Patent Document 1), cyclic olefin random copolymer (A) having a softening temperature of 70 ° C. or higher, and a soft ice temperature of less than 70 ° C. A cyclic olefin based random copolymer composition comprising a soft polymer (B) such as a cyclic polyolefin based random copolymer, and a fatty acid having 5 or more carbon atoms (C) is disclosed.

[0004] Further, according to JP-A-2005-254508 (Patent Document 2), a laminated film including a base material layer and a sealant layer laminated on one surface side of the base material layer is provided. The layer is composed of a polyolefin resin having a melting point of 110 to 220 ° C. as a main component, and the sealant layer is formed of a laminated film containing a cyclic polyolefin resin having a glass transition temperature of 100 to 170 ° C as a main component. A medical container is disclosed. This document describes a sealant layer combining a cyclic olefin-based resin having a glass transition temperature of 100 to 170 ° C. and a cyclic olefin-based resin having a glass transition temperature of less than 100 ° C. Furthermore, according to Japanese Patent Application Laid-Open No. 2005-201987 (Patent Document 3), a print layer is provided on at least one surface of a base film composed of a central layer and surface layers laminated on both sides. A stretch-shrink label is disclosed, wherein the surface layer is composed of an amorphous cyclic olefin polymer and a linear low density polyethylene.

However, when a cyclic olefin-based resin is melt-formed, a gel-like substance (bush) is generated, the surface of the molded article is roughened, and the appearance characteristics are degraded. In particular, when a film is formed by melt-extruding a cyclic olefin-based resin, the surface smoothness (appearance) is reduced by the gel-like substance, and the transparency is also reduced. Therefore, it is not suitable for applications requiring high transparency and appearance characteristics.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-32833 (Claim 1)

Patent Document 2: Japanese Patent Application Laid-Open No. 2005-254508 (Claims 1 and 8, Paragraph Numbers [0036] to [003 8], Examples)

Patent Document 3: Japanese Patent Application Laid-Open No. 2005-201987 (Claim 1)

Disclosure of the invention

Problem that invention tries to solve

Therefore, an object of the present invention is to provide an annular resin composition which has a smooth surface even after melt molding, and a molded article thereof.

Another object of the present invention is a cyclic olefin-based resin composition which is excellent in appearance characteristics such as surface smoothness and transparency, and optical characteristics such as sharpness even when used for injection molding and blow molding, and It is in providing an article.

Still another object of the present invention is to provide a cyclic olefin-based resin which is excellent in appearance characteristics such as surface smoothness and transparency, and optical characteristics such as sharpness even when formed into a film or sheet by extrusion molding. It is an object of the present invention to provide a composition and a film formed of the composition.

Another object of the present invention is to provide a shrink film excellent in appearance characteristics and heat shrinkability.

Means to solve the problem

As a result of intensive studies to achieve the above-mentioned problems, the present inventors found that high molecular weight cyclic olefins The combination of in-based resin and low molecular weight cyclic olefin-based resin has been found to be smooth on the surface of the molded product even after melt-molding, and the present invention has been completed.

That is, the cyclic olefin-based resin composition of the present invention is composed of cyclic olefin-based resin (A1) and low molecular weight cyclic olefin-based resin (A2) having a number average molecular weight of 10000 or less. I hate it! The cyclic olefin-based resin (A1) and the low molecular weight cyclic olefin-based resin (A2) may be a copolymer having polycyclic olefin and chain olefin as a polymerization component. The number average molecular weight of the cyclic olefin-based resin (A1) may be about 15,000 to 200,000 and the number average molecular weight of the low molecular weight cyclic olefin-based resin (A2) may be about 500 to 8,000. Furthermore, the low molecular weight cyclic olefin-based resin (A2) may have a softening point of 70 ° C. or higher and a number average molecular weight of 1000 to 7000. The soft softening point of the low molecular weight cyclic olefin-based resin (A2) may be 10 ° C. or more lower than that of the cyclic olefin-based resin (A1). The proportion of the low molecular weight cyclic olefin-based resin (A2) is about 0.1 to 50 parts by weight with respect to 100 parts by weight of the cyclic olefin-based resin (A1). The resin composition of the present invention may further contain an olefin-based resin (B). The olefin-based resin (B) may be linear low density polyethylene. The proportion of the olefin-based resin (B) is about 1 to about L00 parts by weight with respect to 100 parts by weight of the cyclic olefin-based resin (A1). The resin composition of the present invention may further contain a lubricant (C). The proportion of the lubricant (C) is about 0.01 to 5 parts by weight with respect to 100 parts by weight of the cyclic olefin resin (A1).

The present invention also includes a molded product (for example, an injection molded product, a blow molded product, a film such as a shrink film) formed of at least the above-mentioned cyclic olefin-based resin composition.

Furthermore, in the present invention, a low molecular weight cyclic olefin-based resin (A2) having a number average molecular weight of 10000 or less is added to the cyclic olefin-based resin (A1), and the transparency or surface smoothness of the molded article is obtained. Also included are ways to improve

Effect of the invention

In the present invention, since the low molecular weight cyclic olefin-based resin is contained, the surface of the molded article is smooth even when the composition containing the cyclic olefin-based resin as a main component is melt-formed. In particular, the surface of the molded product is smooth even if it is used for injection molding or blow molding, or formed into a film or sheet, and it is also excellent in appearance characteristics such as transparency and optical characteristics such as sharpness. It can also be used as an optical film such as a liquid crystal protective film, a retardation film, a polarizing film, a polarizing plate protective film, a viewing angle widening film, a diffusion film, an alignment film, a brightness enhancement film, and a reflective film. Furthermore, this resin composition may also be used as a shrink film because it has high heat shrinkability.

Detailed Description of the Invention

The cyclic olefin-based resin composition of the present invention is composed of a cyclic olefin-based resin (A1) and a low molecular weight cyclic olefin-based resin (A2) having a number average molecular weight of 10000 or less. The resin composition of the present invention contains a further amount of olefin resin (B) and lubricant (C).

(A1) Cyclic Olefin-Based Resin

The cyclic polyolefin-based resin (A1) may be a resin having at least a polymerizable cyclic olefin having an ethylenic double bond in the ring as a polymerization component. The cyclic olefin may be a monocyclic or a multivalent ring.

Representative cyclic olefins include, for example, norbornenes, cyclopentadienes or dicyclopentadienes, and 1,4,5,8-dimethanolone obtained by condensation of norbornenes and cyclopentadiene 1 , 2, 3, 4, 4a, 5, 8, 8a クタ ctahydronaphthalenes, hexacyclo [6. 6. 1. 1. 1. 0. 0] heptadecenes 4, 1-butene and cyclopentadiene and force Examples thereof include polycyclic olefins such as 6-ethylbicyclo [2.2. 1] hept-2-ene synthesized.

In addition, cyclic olefin may be substituted with a substituent {eg, a hydrocarbon group [eg, an alkyl group (eg, a C alkyl group such as a methyl group, preferably a C alkyl group), a cycloalkyl

1-10 1-5

Groups (eg, C cycloalkyl groups such as cyclohexyl groups), aryl groups (eg,

5- 10

C aryl groups such as phenyl), alkenyl groups (for example, C alkyl such as propenyl group)

6-102 alkenyl group, etc.), cycloalkenyl group (eg, cyclopentenyl group, cyclo

- Ten

(C cycloalkenyl groups such as xyl group), alkylidene groups (eg, ethylidene)

5- 10

A C alkylidene group such as an alkyl group, preferably an alkylidene group such as

2- 10 2-5

A xy group (for example, a C alkoxy group such as a methoxy group, preferably a C alkoxy group)

1-10 1-6

, Asyl group (eg, C-asyl group such as acetyl group), alkoxycarbonyl group (Eg, c alkoxy-carboyl groups such as methoxycarbo groups), hydroxy

1- 10

Groups, carboxyl groups, amino groups, substituted amino groups, halogen atoms, haloalkyl groups,-heterocyclic groups, cyano groups, oxo groups (= 0), heterocyclic groups (such as nitrogen-containing heterocyclic groups such as pyridyl group) Etc. may be included. The cyclic olefin may have a substituent either alone or in combination of two or more.

Specific examples of cyclic olefins include monocyclic olefins [for example, cycloalkenes (for example, cyclobutenes, cyclopentenes, cycloheptenes, cyclo-

Cycloalkadiene (eg cyclopentadiene etc.)

Ten

Alkadiene) and the like]; bicyclic orefines {eg, bicycloalkenes [eg,

3-10

Rubornens (for example, 2 norbornene, 5-methyl-2 norbornene, 5, 5 or 5, 6 or 6 dimethyl-2 norbornene, 5 ethylidene-2 norbornene, 5 cyano 2 norbornene, 5 methoxy carbo-rou 2 norbornene, 5 phenylalanine 2 C-bicycloalkenes such as norbornene, 5-methyl-5-methoxycarboxyl-2 norbornene, 5, 6 dimethoxycarbo-2 norbornene, 5, 6 di (trifluoromethyl) 2 norbornene, 7-oxo 2-norbornene, etc. Etc], bicycloal force

4-20

[E.g., norbornadienes (e.g., 2,5 norbornadiene, 5 methyl-2, 5 norbornadiene, 5 sianho 2,5 norbornadiene, 5-methoxycarbonyl-2, 5 norbornadiene, 5 pheneiro 2, 5 norbornadiene, 5, 6 — Dimethyl-2,5 norbornadiene, 5, 6 di (trifluoromethyl) 2, 5 norbornadiene, 7 oxo 2 norbornadiene etc) etc. etc., etc.}, tricyclic olefin {eg, tricycloalkene [eg, dihydrodicyclo [eg, C tricycloalkenes such as pentagens (such as dihydrodicyclo pentagen) etc.], tricycloalkadienes [eg

6-25

For example, dicyclopentadienes (such as dicyclopentadiene and methyldicyclopentadiene)

, 卜トリ [4. 4. 0. 12, 5] unde force-3, 7 GEN, 卜シクロ [4. 4. 0. 12, 5] unde car 3, 8-such as C tricycloalkadiene such as GEN ], Etc.}, more than four rings

6-25

Cyclic olefin {eg, tetracyclic olefin [eg, tetracycloalkene (eg, tetracycloalkene [eg, tetracyclo [4. 4. 0. 12, 5. 17, 10]-3 dodecene, 8-methinole tetracyclo [4. 4 12, 5. 17, 10] — 3 dodecene, 8, 9 dimethyl tetracyclo [4. 4. 0. 12, 5. 17 ,, 10] — 3 Dodecene etc. C tetracycloalkene etc. etc.], etc., pentacyclic

8-30

For example, pentacycloalkadiene (eg, C pen such as tricyclopentadiene

10-35 (such as tacycloalkadiene), etc.], hexacyclic olefin [eg, hexacycloalkene (eg, hexacyclo [6. 6. 1. 13, 6. 02, 7. 09, 14]-4-heptadecene) Such as C

12-40 Hexacycloalkene) etc.] and the like. Polycyclic alphane such as

These cyclic olefins can be used alone or in combination of two or more. Among these cyclic olefins, polycyclic olefins such as norbornenes are preferred! /.

The cyclic olefin-based resin may be a homopolymer or copolymer of cyclic olefin (for example, a copolymer of monocyclic and polycyclic olefin, etc.) and a copolymer with cyclic olefin. It may be a copolymer with a polarizable monomer.

[0023] The copolymerizable monomer is not particularly limited as long as it can be copolymerized, and

[Alkenes (eg, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene, 3-acetyl-1-pentene, 4-methyl-1-pentene, 4-methyl] —1—Hexene, 4, 4 Dimethyl- 1-Hexene, 4, 4 Dimethyl- 1-Pentene, 4 Acety- 1 Hexane, 3 Acety- 1 Hexane, 1-Otaten, 1-Decene, 1-Dodecene 1-tetradecene, 1-hexadecene, 1-octadecene, 1 C-alkene such as eicosene), alkadiene (eg, 1, 4

2-20

Hexagen, 4-methyl-1, 4-hexagen, 5-methyl-1, 4-hexagen, non-conjugated C alkadienes such as 1, 7-octadiene, etc., and the like. These

5-20

These copolymerizable monomers can be used alone or in combination of two or more. The copolymerizable monomers may be α-olefins (eg, ethylene, propylene, 1-butene, 1-pentene, 1-pentene, 1-hexenes such as 1-hexenes, particularly C-α-olefins).

2-10 2-6

Yes.

Furthermore, as long as the object of the present invention is not impaired, as a copolymerizable monomer, a polymerizable-trilyl compound (for example, (meth) acrylonitrile etc.), (meth) acrylic monomer (For example, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid etc.), unsaturated dicarboxylic acids or derivatives thereof (maleic anhydride etc.), biphenyl -Esters (eg, acetate, propionate, etc.), conjugated Tagene, isoprene, etc.) may be used. These copolymerizable monomers may be used alone or in combination of two or more.

The proportion of a copolymerizable monomer (for example, a-olefins such as ethylene) in a cyclic polyolefin-based copolymer can be selected within a range of about 0 to 99% by mole of all monomers. , for example, 1 to 95 mole ^_0/0, preferably from 10 to 90 mole ^_0/0, more preferably 20 to 90 mole ^_0/0 may be (in particular 30 to 85 mol%) of about. In particular, when the copolymerizable monomer is ethylene, the proportion of ethylene, from the viewpoint of excellent balance of such appearance characteristics and mechanical properties, for example, 35 to 80 mole ^_0/0, preferably from 40 to 70 mole ⁰ It may be about / ₀ .

Preferred cyclic polyolefin-based resins are copolymers of cyclic olefin and chain alefin, and resins comprising a polycyclic olefin (eg, a di- to hexa-cyclic olefin, etc.) as a polymerization component, in particular, It is a copolymer of cyclic olefin (a monomer having a norbornene skeleton such as the norbornenes and the dicyclopentadienes) and _α -olefin. In particular, copolymers of cyclic olefin and chain olefin (for example, copolymers of a-C olefin and polycyclic olefin such as copolymers of ethylene and norbornene monomers) are

2-4

It also has the properties of an olefin-based polymer (such as an ethylene-based polymer) and a cyclic olefin-based polymer, and a polymer having a high molecular weight can be obtained by adjusting the copolymerization ratio of chain-linked olefin.

The soft melting point of the cyclic polyolefin-based resin (A1) is 70 ° C. or higher, for example, 80 to 250 ^° C., preferably 100 to 230 ^° C., more preferably It is about 120 to 220 ^° C. (especially 130 to 210 ° C.). The softening point can be controlled by adjusting the glass transition temperature, the proportion of the copolymer component, the molecular weight and the like.

Furthermore, in the present invention, the softening point was measured by the thermal deformation behavior of a lmm-thick sheet using a thermal / stress / strain measurement device (manufactured by Seiko Instruments Inc., TMAZSS 100). In other words, place a quartz needle on a sheet, apply 49 g load, raise the temperature at 5 ° C / min, and let the temperature at which the needle penetrates 0.635 mm be the soft spot. .

The cyclic olefin-based resin (A1) is a high molecular weight cyclic olefin-based resin having a number average molecular weight of 10000 or more. The number average molecular weight of the cyclic olefin-based resin (A1) is, for example, 15,000 to 2,000,000, preferably <20000 to 100000, further preferably <30000 to 80000 40000 to 70000).

These cyclic olefin-based resins (A1) can be used alone or in combination of two or more. For example, when the molecular weight of the cyclic olefin-based resin to be used is relatively low, it can be combined with a higher molecular weight cyclic olefin-based resin to compensate for practical strength such as impact strength and bending strength. Thus, in the case of combining a plurality of cyclic olefin-based resins (A1), it is desirable that the copolymer composition of each resin be the same, but the composition is different! Do not lose sex! /, Preferred to combine in proportion ヽ

The cyclic olefin-based resin (A1) may be a resin obtained by addition polymerization, or may be a resin obtained by ring-opening polymerization (ring-opening metathesis polymerization, etc.). The cyclic olefin-based resin (eg, a resin obtained by ring-opening metathesis polymerization) may be a hydrogenated hydrogenated resin. The cyclic olefin-based resin may be crystalline or non-crystalline resin, and may usually be non-crystalline resin. The cyclic olefin-based resin (A1) can be produced by a conventional polymerization method (for example, addition polymerization using a Ziegler-type catalyst, addition polymerization using a meta-pore type catalyst, ring-opening metathesis polymerization using a metathesis polymerization catalyst, etc. Prepared according to).

(A2) Low Molecular Weight Cyclic Olefin-Based Resin

Examples of the low molecular weight cyclic olefin-based resin (A2) include the cyclic olefin-based resins exemplified in the section of the cyclic olefin-based resin (A1). Among these cyclic olefin-based resins, it is preferable to use a resin of the same or the same type as that of the cyclic olefin-based resin (A1) from the viewpoint of compatibility and the like.

[0033] When the low molecular weight cyclic polyolefin-based resin is a copolymer, the proportion of copolymerizable monomers (for example, _α- modified olefins such as ethylene) is 0 to 99 mol of all monomers. in view of the force appearance properties that can be selected from ^_0/0 the range of about, for example, 50 to 99 mol%, preferably about 55 to 95 mol%. In particular, when the copolymerizable monomer is ethylene, the proportion of ethylene, in view of appearance characteristics, e.g., 60 to 90 mole ^_0/0, even preferably 70 to 85 mole ^_0/0 approximately Yo!

The soft softening point of the low molecular weight cyclic olefin-based resin (A2) is 70 ° C. or higher. , 75 to 200 ^o C, preferably 80 to 150 ^o C, more preferably 85 to 130 ^o C (special 90 to L IO

° C). If the softening point is too low, the mechanical properties of the resin composition will be reduced.

Furthermore, the soft point of the low molecular weight cyclic olefin resin (A2) is a cyclic olefin resin (A2).

For example, lower than the soft softening point of A1) is preferably 10 ° C. or higher (eg, 10 to 150 ° C.), preferably 20 ° C. or higher (eg, 20 to 140 ° C.) And more preferably 25 ° C. or more (eg, 25 to 130 ° C.) lower.

The number average molecular weight of the low molecular weight cyclic olefin-based resin (A2) is 10000 or less, for example, 500 to 8000, preferably <1000 to 7000, more preferably <1500 ~ 6000 (special [this 20

It is about 00 to 5000).

The difference in the number average molecular weight between the high molecular weight cyclic olefin-based resin (A1) and the low molecular weight cyclic olefin-based resin (Α2) can be selected from the range of about 1000 to 200000, for example,

150000, preferably <20000 to 100000, more preferably <30000 to 80000.

The proportion of the low molecular weight cyclic olefin-based resin (Α2) is, for example, 0.1 to 50 parts by weight, preferably 0.5 to 45 parts by weight with respect to 100 parts by weight of the cyclic olefin-based resin (A1). Parts, more preferably about 1 to 40 parts by weight (especially 3 to 30 parts by weight). In the present invention, by using a low molecular weight cyclic olefin-based resin (Α2) at such a ratio, the surface smoothness of the film is improved, and at the same time, the optical characteristics such as transparency, appearance characteristics and sharpness of the film are improved. It can be improved. If the proportion of the low molecular weight cyclic olefin-based resin (Α2) is too high, mechanical strength such as tensile elongation at break will decrease, while if it is too low, surface smoothness will decrease.

The cyclic olefin-based fat composition may exhibit a plurality of (at least two) separated peaks in gel permeation chromatography (GPC). For example, in GPC, at least one peak in the region corresponding to high molecular weight cyclic olefin resin (A1) and at least one in the region corresponding to low molecular weight olefin resin (Α2) It may show a peak.

(Β) Olefin-based resin

Olefin-based resins (Β) include homopolymers or copolymers of olefin. In the present invention, olefin-based resin means non-cyclic olefin-based resin, and as olefin, For example, the chain olefins exemplified in the section of cyclic olefin-based resin (Al), such as ethylene, propylene, 1-butene, isobutene, 4-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, etc. a —C-orephine (preferably a-C-orephine,

2-10 2-8

More preferably, (X-C orefin) and the like can be mentioned. These are not alone

2-4

Or in combination of two or more. Of these olefins, preference is given to including ethylene, propylene, in particular at least ethylene.

The olefin-based resin (榭) may be a copolymer of olefin and a copolymerizable monomer! / ヽ. As the copolymerizable monomer, the polymerizable ditolyl compounds exemplified in the section of the cyclic olefin-based resin (A1), (meth) acrylic monomers, unsaturated dicarboxylic acids or derivatives thereof, vinyl esters, Dienes, for example, (meth) acrylic acid C alkyl esters such as methyl (meth) acrylate and hydroxyethyl (meth) acrylate;

1-6

And vinyls such as butadiene and isoprene. The copolymerizable monomers can be used alone or in combination of two or more. Ratio of the copolymerizable monomer is 0-50 molar total monomer ^_0/0, preferably from 0.1 to 25 mole ^_0/0, more preferably about 1 to 10 mole ^_0/0.

Examples of olefin-based resins (eg, polyethylene-based resins) [eg, low, medium or high density polyethylene, linear low density polyethylene, ethylene propylene copolymer, ethylene-butene 1 copolymer, Ethylene propylene-butene 1 copolymer, ethylene (4-methylpentene 1) copolymer, etc.], polypropylene-based resins (eg, polypropylene, propylene-ethylene copolymer, propylene-butene 1 copolymer, propylene ethylene-butene 1) copolymers of propylene containing 80 wt ^_0/0 or more propylene Ren a Orefuin copolymer etc.), poly (methyl pentene 1)榭脂like are Ru mentioned. As the copolymer, for example, ethylene (meth) atalylate copolymer such as ethylene / vinyl acetate copolymer, ethylene (meth) acrylic acid copolymer or ionomer thereof, ethylene acrylic acid ethyl copolymer, etc., maleic anhydride An example is graft polypropylene.

[0043] The copolymer (copolymer of olefins and copolymer of olefin and copolymer monomer) includes a random copolymer, a block copolymer, or a graft copolymer. Ru.

These olefin-based resins can be used alone or in combination of two or more. In the present invention, of these olefin-based resins, polyethylene-based resins such as low density polyethylene (LDPE) and linear low density polyethylene (LLDPE), particularly linear low density polyethylene (LLDPE), are used. preferable. The density of low-density polyethylene or linear low density ^{polyethylene, 0. 9~0. 95g / cm 3} , preferably 0. 905~0. 945g / cm ^3, more preferably 0. 91~0. 94gZcm ³ about It is.

In the present invention, by using the olefin-based resin (B), the moldability, flexibility, elongation at break, impact strength and the like of the cyclic olefin-based resin composition can be improved. In particular, by using a polyethylene-based resin such as linear low density polyethylene, the surface smoothness and transparency of the molded article can be improved.

The proportion of olefin-based resin (B) is, for example, 1 to: parts by weight of LOO, preferably 5 to 80 parts by weight, and more preferably 10 parts by weight with respect to 100 parts by weight of cyclic olefin-based resin (A1). ~ 70 parts by weight

(Especially 20 to 50 parts by weight).

(C) Lubricant

In the present invention, by using a lubricant (C) in addition to the low molecular weight cyclic olefin-based resin, the flowability of the resin composition can be enhanced, and the surface smoothness of the film or sheet can be improved.

The lubricant (C) includes compounds having a low molecular weight hydrocarbon backbone, such as waxes and fats.

Examples of the waxes include aliphatic hydrocarbon waxes (polyethylene wax, polyethylene copolymer wax, polypropylene waxes and other polyvinyl alcohol waxes, and polypropylene waxes).

2-4

Raffin wax, microcrystalline wax and the like), vegetable or animal waxes (eg, power wax, beeswax, beeswax, shellac wax, montan wax and the like) and the like. These waxes can be used alone or in combination of two or more.

[0050] Examples of lipids include, for example, higher fatty acids (for example, C-saturates of purilic acid, purinic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arabic acid, behenic acid, etc.

8-35 F fatty acid, C-unsaturated fatty acid such as normitoleic acid, oleic acid, erucic acid, etc. , Higher fatty acid salts (eg, barium laurate, zinc laurate, calcium stearate)

, Zinc stearate, metal salts of C fatty acids such as magnesium stearate, etc.)

8-35

Fatty acid ester (for example, C fatty acid such as glycerin fatty acid ester, pentaerythritol fatty acid ester, diglycerin fatty acid ester, polyglycerin fatty acid ester

8-35 esters, etc.), higher fatty acid amides (eg, stearic acid amide, C fatty acid amide such as erucic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide,

8-35

And alkylene bis fatty acid amides such as ethylene bis hydroxy stearamide and the like.

These lubricants can be used alone or in combination of two or more. Among these lubricants, lipids, in particular, C oils such as lauric acid, palmitic acid, stearic acid and behenic acid are used.

C-saturated fats such as 8-35 sum fatty acid, calcium stearate and magnesium stearate

8-35 Metal salts of acid, pentaerythritol C such as pentaerythritol stearic acid ester

Preferred are 8-35 saturated fatty acid esters, and alkylene bis fatty acid amides such as ethylene bis stearic acid amide and ethylene bis hydroxy stear phosphoric acid amide.

The proportion of the lubricant (C) is, for example, 0. 0. 100 parts by weight of the cyclic olefin-based resin (A1).

The amount is about 0.1 to 5 parts by weight, preferably about 0.2 to 3 parts by weight, and more preferably about 0.03 to 2 parts by weight (particularly about 0.05 to 1 part by weight).

The cyclic olefin-based fat composition of the present invention may further contain conventional additives such as plasticizers or softeners, colorants, dispersants, mold release agents, stabilizers (hindered phenol-based antioxidants) Agents, phosphorus-based antioxidants, antioxidants such as sulfur-based antioxidants, UV absorbers, heat stabilizers, etc., antistatic agents, flame retardants, antiblocking agents, crystal nucleation agents, fillers It may contain particulate filler such as silica and talc, fibrous filler such as glass fiber and carbon fiber, and the like. These additives may be used alone or in combination of two or more.

The proportions of these additives are not particularly limited as long as they are selected according to the type, but 0.10 to about the LOO parts by weight with respect to 100 parts by weight of the cyclic alpha-resin (A1). For example, about 0.1 to 50 parts by weight, preferably about 0.5 to 30 parts by weight.

[Crystalline Olefin-Based Resin Composition and Molded Article Thereof] The cyclic olefin-based resin composition of the present invention is excellent in various properties such as optical properties, appearance properties, chemical resistance, moisture resistance, mechanical properties, electrical properties, etc., so mechanical parts, electric or electronic parts, optical parts. It can be used as various types of molded products such as parts, various molded products such as containers, films or sheet-like molded products. Such molded articles can be formed by conventional molding methods such as injection molding, extrusion molding, blow molding, vacuum molding, profile molding, injection pressing, press molding, gas injection molding, compression molding, and the like. And manufacturing methods such as transfer molding.

In particular, the cyclic olefin-based resin composition of the present invention may be used as injection molding, blow molding, extrusion molding or the like because the surface of the molded article is smooth even after melt molding. For example, since the surface smoothness and transparency of molded articles are high even after injection molding or blow molding, three-dimensional molded articles such as lenses and containers may be molded by these molding methods. . Furthermore, the cyclic olefin-based resin composition of the present invention may form a film or a sheet, since it has high transparency and appearance characteristics, even if it is extruded.

The molded article of the present invention has high transparency, for example, in the case of a film, the haze (total haze) is, for example, 0.1 to 30%, preferably 0.05 to 20%, and more preferably 0. 1-15% (especially 0.2-13%) The haze inside the film (the internal haze causing scattering inside the layer) is, for example, 0.01 to 20%, preferably 0.005 to 15%, more preferably 0.01 to 10% (in particular, 0.2 to 8%). Since the film of the present invention has high surface smoothness, it is excellent in transparency in which the difference between the internal haze and the total haze is small.

The internal haze may be, for example, white oil (eg, Cristol J-352, manufactured by Ekson Mobil, etc.) or ethylene glycol in a cell having a predetermined optical path length (eg, 1 cm) in advance. Etc. to measure the haze, immerse the film in this cell, measure the haze, and calculate the difference between the two.

The molded article of the present invention is excellent in surface gloss. For example, in the case of a film, the surface gloss (daros) measured at an angle of 60 ° according to JIS K 7105 is, for example, 50 to 300, preferably 70. ~ 280, more preferably, this is about 80 to 250 (specially 100 to 200).

The molded article of the present invention has high surface smoothness. For example, in the case of a film, the average value of the surface roughness (center line average roughness Ra) is, for example, 0.01 to 1 μm, preferably 0. 03 to 0. 8 m, More preferably, it is about 0.50 to 0. (especially about 0. 1 to 0. 3 m).

The molded article of the present invention is also highly sharp. For example, in the case of a film, the image (transmission image) sharpness is preferably 10 to 99% when an optical comb having a width of 0.5 mm is used. Is preferably about 15 to 98%, more preferably about 20 to 97% (especially 25 to 95%).

Image sharpness is a measure that quantifies the blur or distortion of light transmitted through a film. According to JIS K 7105, the image freshness is measured through the optical comb moving the transmitted light from the film, and the value is calculated from the light intensity of the light and dark portions of the optical comb. That is, when the film blurs the transmitted light, the image of the slit formed on the optical comb becomes thick, so the light quantity at the transmission part becomes 100% or less, while the light leaks at the non-transmission part. It becomes above. The value C of the image definition is defined by the following equation from the maximum value M of the transmitted light of the transparent part of the optical comb and the minimum value m of the transmitted light of the opaque part.

C (%) = [(M−m) / (M + m)] × 100

That is, the closer the value of C approaches 100%, the smaller the image blur caused by the film [References: Suga, Mitamura, Painting Technology, July 1985].

[Film or Sheet]

The thickness of the film or sheet formed of the cyclic olefin-based resin composition of the present invention can be selected according to the application, and for example, 5-500 / ζπι, preferably 10-300 / ζπι, more preferably Or it may be about 20 to 200 μm (especially 50 ~ 150 ^ m)!ヽ.

The surface of the film of the present invention may be surface-treated by a conventional surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone or ultraviolet radiation treatment and the like.

The film of the present invention may be laminated with other thermoplastic resin films (for example, polyester resin, polyamide resin, olefin resin film, etc.), if necessary. In particular, it may be laminated with a film or sheet formed of olefin-based resin, because of its excellent adhesion to olefin-based resin.

Furthermore, among the films, since the resin composition of the present invention has high heat shrinkage, it is heated and shrunk to adhere the object (solid article such as a container or a tool) by covering it. The film may be used as a so-called shrink film. The shrink film may be a laminate with another thermoplastic resin film, for example, the cyclic fiber of the present invention It may be a laminate with an olefin resin film in which a layer formed of an in-based resin composition is used as a surface layer (outer layer) or a core layer (inner layer).

[0068] The film of the present invention may form another functional layer. As a functional layer, for example, gas noble layer (oxygen gas noble, water vapor gas barrier layer, etc.), antistatic layer, sliding layer, antifogging layer, printed layer, vapor deposition layer (metal oxide deposit vapor deposition layer, etc.) Etc.

The film of the present invention may be an unstretched film, but may be a stretched (or stretched, usually uniaxial or biaxial) stretched film. For the stretched film, a conventional film production method, for example, a mixed or kneaded resin or a composition thereof (a resin constituting the core layer or a composition thereof) is supplied to a single screw or twin screw extruder, Melt-kneading and extruding from a die [flat-like, T-like (T-die), cylindrical (circular die), etc.] to form, the obtained unstretched film is uniaxially or biaxially stretched by a conventional method. It can be prepared by

In particular, in the case of a shrink film, in order to enhance heat shrinkability, it is preferable to conduct stretching at a high stretching ratio. Specifically, the stretching ratio can be selected, for example, from the range of about 1.5 to 30 times, preferably about 4 to 8 times, and more preferably about 5 to 7 times.

The stretched film also has high heat shrinkability. For example, when the film is immersed in warm water at 90 ° C. for 10 seconds, the thermal shrinkage (or its absolute value) in the film take-up direction (MD direction or longitudinal direction or one direction) is, for example, 15 to 50% Preferably, it is about 18 to 40%.

Industrial applicability

The cyclic olefin-based resin composition of the present invention is excellent in transparency, chemical resistance, moisture resistance, mechanical properties and the like, and thus an optical film (a liquid crystal protective film, a retardation film, a polarizing film, a polarizing film Plate protective film, viewing angle widening film, diffusion film, orientation, brightness enhancement film, reflection film etc., optical parts (optical parts such as camera or video, lenses, panels, optical recording materials etc.) parts for electric or electronic (Connector, film capacitor, insulating material (insulation layer), equipment for semiconductors or packaging material), medicine or medical equipment supplies (container for medicine, syringe, cell for blood test, collection bin, beaker, cylinder, syringe) Etc.), experimental instruments (optical cells, optical instruments, beakers, flasks etc.), containers or packaging materials (food and medicines, etc. Film, beverage tank, such as cosmetics capacity dexterity cap) can be used as such. [0073] Furthermore, in addition to transparency and appearance characteristics, heat shrinkability is also high, so shrink films, for example, shrink films for beverages etc. (shrink caps for protection of corks of wine bottles, shrink films for PET bottles Etc.), sleeve films (battery, office automation equipment, sleeve films of electric and electronic devices or parts, etc.) and the like.

Example

The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples. The materials used in Examples and Comparative Examples are as follows, and the evaluation items were measured by the following methods.

[Material]

COC (Al-1): cyclic olefin resin, manufactured by Topas Advanced Polymers GmbH, trade name "TOPAS9506", number average molecular weight 66000, heat distortion temperature (softening point) 134

. C, glass transition temperature 70 ° C., density 1.02

COC (Al-2): cyclic olefin resin, manufactured by Topas Advanced Polymers GmbH, trade name "Ding-838007", number average molecular weight 51000, heat distortion temperature 138 ° C, glass transition temperature 80 ° C, density 1. 02

COC (Al-3): cyclic olefin resin, manufactured by Topas Advanced Polymers GmbH, trade name "TOPAS6013", number average molecular weight 47000, heat distortion temperature 206 ° C, glass transition temperature 130 ° C, density 1.02

COC (Al-4): low molecular weight cyclic olefin resin, manufactured by Topas Advanced Polymers GmbH, TOPAS 4017, number average molecular weight 15000, glass transition temperature 140. C, heat distortion temperature 190 ° C, density 1.02

COC (A2-l): low molecular weight cyclic olefin resin, manufactured by Topas Advanced Polymers GmbH, TOPASTM, number average molecular weight 4400, glass transition temperature 67 ° C., thermal deformation temperature 96 ° C., density 1. 02

COC (A2-2): Low molecular weight cyclic olefin resin, TOPAS Advanced Polymers GmbH, TOPAS TMX1T2, number average molecular weight 2400, glass transition temperature 57 ° C., heat distortion temperature 80 ° C. LLDPE (Bl): Linear low density polyethylene, manufactured by Prime Polymer Co., Ltd., trade name "EVOLIE SP2320", MFR: 1. 9 g ZlO, density 0.92, α-olefin: hexene

LLDPE (B2): linear low density polyethylene, manufactured by Prime Polymer Co., Ltd., trade name “Neo Zettas 043L”, MFR: 4 g ZlO, density 0.92 α-aref: butene

LLDPE (B3): Linear low density polyethylene, manufactured by Prime Polymer Co., Ltd., trade name "Mor Tech 0258CN", MFR: 2. lg / 10 min, density 0.93, α-olefin: Othene lubricant: ethylene bis Stearic acid amide.

[Method of Measuring Molecular Weight]

The number average molecular weight of cyclic olefin-based resin was measured under the following conditions.

(Measurement conditions)

Device: Shodex SYSTEM-21 (Rl)

Solvent: Toluene (Nacalai HPLC grade)

Column: Polymer Laboratories, MIXED— C (1)

Flow rate: 0.8 ml Z min

Temperature: 40 ° C

Sample concentration: 0.2 w Zv% (pre-filtered with a membrane filter of 0.2 m) Injection volume: 100 1

Standard sample: Molecular weight: 1090000, 706000, 427000, 190000, 96400, 37900, 18100, 10200, 5970, 2630, 1050, 500 PS (polystyrene with a concentration of 0.1 lw Zv)

Analysis: Evaluate PS converted molecular weight

Number of repeated measurements: 2 times.

[Softening point]

It measured based on the heat | fever deformation | transformation behavior of thickness lmm using a thermomechanical analyzer (made by Seiko Electronic Industry Co., Ltd., TMAZSS 100). Specifically, a sheet of 1 mm in thickness is placed on the sample holder, a quartz needle is placed, the sample is heated at 5 ° CZ while applying a load of 49 gf (0.48 N), and the needle is 0.65 mm The temperature which penetrated was made into the soft spot.

[0079] [Film Appearance] The appearance of the film was visually observed and evaluated according to the following criteria.

0080: No occurrence of gel (bump) on film surface! /,

○: Slight occurrence of gel (bump) on film surface

Δ: generation of gel (bump) on film surface

X: Occurrence of a large number of gels (bubbling) is observed on the film surface.

[Haze]

The haze was measured using NDH-300A haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7105.

[Glossy]

The dalos was measured at an angle of 60 ° in the MD direction in accordance with JIS K7105.

[Surface Roughness]

The center line average roughness Ra was measured in accordance with JIS B 0601 using a surface roughness profiler (Surfercom 1400A, manufactured by Tokyo Seimitsu Co., Ltd.) to measure the center line average roughness Ra of the substrate surface. .

[Definition]

The image sharpness was measured using an optical comb of 0.5 mm width in parallel with the MD direction using an image clarity measuring device (ICM-1DP, manufactured by Suga Test Instruments Co., Ltd.).

[Tensile test]

A test piece is punched out of a sheet into a dumbbell shape and pulled to break with a tensile tester, and the tensile elongation at break, maximum point strength, and initial modulus (kgfZcm ² ) are evaluated according to JIS K 7113.

Example 1

0.1 parts by weight of a lubricant was added to 100 parts by weight of a mixture of 95% by weight of cyclic olefin-based resin COC (A1 1) and 5% by weight of low molecular weight cyclic olefin-based resin (A2-1). The blend was extruded into a film of about 100 / z m thickness using a single screw extruder (LZD = 28, compression ratio 1.8). The obtained film was cut into a predetermined shape, and the characteristics were evaluated. The results are shown in Table 1.

Examples 2 to 7 and Comparative Examples 1 to 3

A film was produced in the same manner as in Example 1 according to the formulation shown in Table 1. Evaluate film characteristics The results are shown in Table 1.

[table 1]

As apparent from the results in Table 1, the film of Example 17 has a smooth surface and transparency. Excellent in appearance characteristics and high in mechanical characteristics. On the other hand, in the films of Comparative Examples 1 to 3, gel is generated and the appearance is lowered.

Example 8

Cyclic olefin resin COC (Al-1) 68. 3 parts by weight, low molecular weight cyclic olefin resin (A2-1) 3.1 parts by weight, linear low density polyethylene LLDPE (B1) 27. 6 To the mixture with parts by weight, 0.1 part by weight of stearic acid was added. This blend was extruded into a film about 100 m thick using a single screw extruder (LZD = 28, compression ratio 1.8). The obtained film was cut into a predetermined shape, and the characteristics were evaluated. The results are shown in Table 2.

Examples 9 to 14 and Comparative Examples 4 to 6

A film was produced in the same manner as in Example 8 according to the formulation shown in Table 2. The results of evaluation of the film properties are shown in Table 2.

[Table 2]

As apparent from the results of Table 2, the films of Examples 8 to 11, 13 and 14 have smooth surfaces, excellent transparency and appearance characteristics, and high mechanical characteristics. The film of Example 12 has reduced appearance characteristics and excellent force transparency and mechanical properties. On the other hand, in the films of Comparative Examples 4 to 6, gel is generated and the appearance is lowered. Example 15

Cyclic Orefin system榭脂COC (A1 - 1) and 10 weight ^{_{0/0, (1 3 A}} ) and 80 wt% cyclic Orefin system榭脂COC, low molecular weight cyclic Orefin resin (A2- 1) with 10 wt% To 100 parts by weight of the mixture, 0.1 part by weight of a lubricant was added. The blend was extruded into a film of about 120 μπ 厚 thickness using a single screw extruder (LZ D = 28, compression ratio 1.8). The obtained film was cut into a predetermined shape, and the characteristics were evaluated. The results are shown in Table 3.

Examples 16 to 17 and Comparative Example 7

A film was produced in the same manner as in Example 15 according to the formulation shown in Table 3. Table 3 shows the results of evaluating the film characteristics.

[Table 3]

Table 3

As apparent from the results of Table 3, the films of Examples 15 to 17 have smooth surfaces, excellent transparency and appearance characteristics, and high mechanical characteristics. On the other hand, in the film of Comparative Example 7, Sharpness is low.

Claims

The scope of the claims

[I] It is composed of cyclic olefin-based resin (A1) and low molecular weight cyclic olefin-based resin (A2) having a number average molecular weight of 10000 or less! A spongy cyclic olefin resin composition.

[2] The resin according to claim 1, wherein the cyclic olefin-based resin (A1) and the low molecular weight cyclic olefin-based resin (A2) are copolymers comprising polycyclic olefin and chain olefin as a polymerization component. Composition.

[3] The resin according to claim 1, wherein the number average molecular weight of the cyclic olefin resin (A1) is 15,000 to 200,000, and the number average molecular weight of the low molecular weight cyclic olefin resin (A2) is 500 to 8,000. Composition.

[4] Low molecular weight cyclic olefin-based resin (A2) has a softening point of 70 ° C. or higher and a number average molecular weight 1

The resin composition according to claim 1, having a weight of 4,000 to 7,000.

[5] The resin composition according to claim 1, wherein the soft softening point of the low molecular weight cyclic olefin-based resin (A2) is 10 ° C. or more lower than that of the cyclic olefin-based resin (A1).

[6] The resin composition according to claim 1, wherein the proportion of the low molecular weight cyclic olefin-based resin (A2) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the cyclic olefin-based resin (A1). .

[7] The resin composition according to claim 1, further comprising olefin resin (B).

[8] The resin composition according to claim 7, wherein the olefin-based resin (B) is linear low density polyethylene.

[9] Relative force of olefin-based resin (Β) For 100 parts by weight of cyclic olefin-based resin (A1),

The resin composition according to claim 7, which is 1 to 100 parts by weight.

[10] The resin composition according to claim 1, further comprising a lubricant (C).

[II] The relative strength of the lubricant (C) The resin composition according to claim 10, which is 0.1 to 5 parts by weight with respect to 100 parts by weight of the cyclic olefin-based resin (A1).

[12] A molded article formed of at least the resin composition according to claim 1.

[13] An injection molded article formed of at least the resin composition according to claim 1.

[14] A blow molded article formed of at least the resin composition according to claim 1.

[15] A film formed of at least the resin composition according to claim 1.

[16] A shrink film formed of at least the resin composition according to claim 1. A method of improving the transparency or surface smoothness of a molded article by adding a low molecular weight cyclic olefin-based resin (A2) having a number average molecular weight of 10000 or less to a cyclic olefin-based resin (Al).