JP2001055451A - Synthetic paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a synthetic paper which comprises the sheet or film-like formed product of a resin composition comprising a cyclic olefinic resin and another specific resin, is opaque, and has excellent mechanical strengths, excellent surface smoothness, improved tear resistance and improved bendability. SOLUTION: This synthetic paper comprises the sheet or film-like formed product of a resin composition which comprises (A) at least one kind of cyclic olefinic resin selected from the group consisting the following components (i) to (iv): (i) an α-olefin.cyclic olefin random copolymer obtained by copolymerizing a 2 to 20C α-olefin with a cyclic olefin of formula I [(n) and (q) are each 0 or 1; (m) is 0, 1 or larger; R1 to R18, Ra and Rb are each H, a halogen or a hydrocarbon group] or formula II [(p) and (q) are each 0, 1 or larger; (m) and (n) are each 0 to 2; R1 to R19 are H, a halogen, an aliphatic hydrocarbon group or the like], (ii) the ring-opened polymer or copolymer of the cyclic olefin of formula I or formula II, (iii) the hydrogenation product of the ring-opened polymer or copolymer, and (iv) the grafted product of the component (i), (ii) or (iii), and (B) another resin having a difference of >=0.02 between the refractive indexes of the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic paper using a sheet or film-like molded article, and more particularly, to a synthetic paper using the same.
The present invention relates to a synthetic paper having toughness and excellent smoothness.

[0002]

BACKGROUND OF THE INVENTION Conventionally, synthetic paper has been produced from synthetic resin as a main raw material and given the appearance (whiteness), opacity, writability, printability and the like of paper made from wood pulp. ing. Synthetic paper is superior in strength and water resistance to natural paper, and is used in various fields such as base paper for information paper, commercial printed matter, map paper, etc.It is not just a substitute for natural paper, it has special functions, The market is expanding as a material with characteristics.

[0003] The method of producing synthetic paper is divided into a film method and a fiber method. The film method is superior in productivity to the fiber method and more advantageous in cost than the fiber method. In the film method, additives are added to the synthetic resin and filler and mixed,
After melt-kneading with an extruder, there is an internal paper method of extruding from a die slit to form a film, and a surface coating method of pigment coating the surface using a synthetic resin film as a base, but both are made from synthetic resin films Become.

By the way, opaque polyolefin-based films have been used widely as synthetic papers because of their complete water resistance. For the production of this polyolefin-based white film, inorganic fillers and pigments such as calcium carbonate,
Alternatively, a method of adding a crystalline polyester or the like to a polyolefin resin such as polyethylene or polypropylene, a method of adding inorganic solid particles to a polyolefin, and then stretching to form a void may be used.

However, these methods have problems that the toughness of the film is reduced and the smoothness of the film surface is poor. In addition, since solids that do not melt even at the extrusion molding temperature are mixed, troubles may occur during production such as clogging of an extruder screen, and improvement has been demanded.

Accordingly, the present applicants have previously described Japanese Patent Application Laid-Open No. 8-73.
No. 618 discloses, as an opaque polyolefin film used for synthetic paper or the like, a film obtained by stretching a raw sheet made of a composition obtained by adding a cyclic olefin-based resin to a crystalline polyolefin at 20% by weight or less. This film has low light transmittance, is opaque, has excellent mechanical strength and surface smoothness, and is a useful film as synthetic paper. However, it is inferior in tearing property and folding property, and improvement has been demanded.

[0007]

SUMMARY OF THE INVENTION The present invention has been made under the above-mentioned background, and is opaque, has excellent mechanical strength and surface smoothness, and has improved tearability and bendability. The purpose of the present invention is to provide a synthetic paper.

[0008]

According to the present invention, there is provided a synthetic paper comprising:
[A] at least one cyclic olefin resin selected from the group consisting of the following [A-1], [A-2], [A-3] and [A-4]; [B] the above [A] And a resin or sheet-like molded product of a resin composition with another resin having a difference in refractive index of 0.02 or more.

[A-1] α-olefin / cyclic olefin random obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms with a cyclic olefin represented by the following formula (I) or (II) Copolymer,

Embedded image (In the formula, n is 0 or 1, m is 0 or an integer of 1 or more, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{1 5} to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, and also monocyclic or polycyclic have a double bond good, and R ¹ is ⁵ and the R ^{1 6,} or R ^{1 7} and R ^{1 8} and in may form an alkylidene group.)

[0010]

Embedded image (Where p and q are 0 or an integer of 1 or more;
And n is 0, 1 or 2, each R ¹ to R ^{1 9} independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group,
Alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ^{1 0} are attached,
The carbon atom to which R ^{1 3} or R ^{1 1} is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when the ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form a monocyclic or polycyclic aromatic ring bonded to each other. ),

[A-2] A ring-opened polymer or copolymer of a cyclic olefin represented by the above formula (I) or (II),
3] A hydride of the above-mentioned [A-2] ring-opening polymer or copolymer, and [A-4] a graft-modified product of the above [A-1], [A-2] or [A-3].

In a preferred embodiment of the present invention, the resin composition contains the other resin component [B] in a proportion of 1 to 100 parts by weight based on 100 parts by weight of the cyclic olefin resin [A]. Is desirable. In a preferred aspect of the present invention, the resin [B] is desirably polymethyl methacrylate.

In the synthetic paper of the present invention, the sheet or film-like molded article constituting the synthetic paper may be obtained by stretching a sheet or film obtained by extruding the resin composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, [A] a cyclic olefin resin, [B] other resin components, their resin compositions, and sheets or films of the resin compositions constituting the synthetic paper according to the present invention. The molded article and the synthetic paper made therefrom will be specifically described. First, [A] the cyclic olefin-based resin will be described.

[A] Cyclic olefin resin In the present invention, the cyclic olefin resin [A] is
[A-1]: a random copolymer of an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula (I) or (II), [A-2]: a random copolymer of the following formula (I ) Or a ring-opening polymer or copolymer of a cyclic olefin represented by (II),
[A-3]: a hydride of the above [A-2] ring-opening polymer or copolymer, and [A-4]: a above [A-1], [A-2] or [A-3] At least one selected from the group consisting of graft-modified products of the above is used.

The cyclic olefin resin used in the present invention has a glass transition temperature (Tg) measured by DSC of 70 ° C.
Or more, more preferably 70 to 2
The temperature is 50 ° C, and particularly preferably 120 to 180 ° C.

The cyclic olefin resin is amorphous or low-crystalline, and has a crystallinity, as measured by X-ray diffraction, of usually not more than 20%, preferably not more than 10%, more preferably not more than 10%. 2% or less.

The intrinsic viscosity [η] of this cyclic olefin resin measured at 135 ° C. in decalin is usually 0.01 to 0.01.
20 dl / g, preferably 0.03 to 10 dl / g
g, more preferably 0.05 to 5 dl / g. 260 ° C., 2.16 load according to ASTM D1238.
The melt flow index (MFR) measured in kg is typically 0.1
To 200 g / 10 min, preferably 1 to 100 g / min.
10 minutes, more preferably 5 to 50 g / 10 minutes.

The softening point of the cyclic olefin resin is determined by the softening point (TMA) measured with a thermal mechanical analyzer.
Is usually 30 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 to 260 ° C.

Here, the cyclic olefin represented by the formula (I) or (II) that forms the cyclic olefin resin [A] used in the present invention will be described. Cyclic olefin The cyclic olefin used in the present invention is represented by the following formula (I) or (II).

Embedded image

In the above formula (I), n is 0 or 1,
m is 0 or an integer of 1 or more, and q is 0 or 1. When q is 1, R ^a and R ^b are each independently an atom or a hydrocarbon group shown below, and q
Is 0, the respective bonds are combined to form a 5-membered ring.

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,
It is a bromine atom or an iodine atom.

The hydrocarbon groups each 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. And the aromatic hydrocarbon group includes a phenyl group and a naphthyl group.
These hydrocarbon groups may be substituted with a halogen atom. In addition the above formula (I), the attached R ^{1 5} to R ¹⁸ are each (jointly with each other) may form a monocyclic or polycyclic, moreover, monocyclic or formed in this manner The polycyclic ring may have a double bond.

[0024]

Embedded image In the formula (II), p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2. Also, R ^{1 to} R ^1
9 is 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). As the hydrocarbon group, each independently represents an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms,
15 cycloalkyl groups or aromatic hydrocarbon groups. 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 an aromatic hydrocarbon group is 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.

[0027] Here, the carbon atom to which R ⁹ and R ^{1 0} is attached, the carbon atom to which R ^{1 3} carbon atoms or R ^{1 1} are bonded is bonded, directly or number of carbon atoms 1 to
And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are linked via an alkylene group, a group represented by R ⁹ and R ^{1 3} is, or a group represented by R ^{1 0} and R ^{1 1,} together jointly, a methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or propylene group _{(-CH 2 CH 2 CH 2 -} ) to form one alkylene group of the.

Furthermore, when ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form an aromatic ring bonded to a monocyclic or polycyclic one another . As monocyclic or polycyclic aromatic ring in this case, for example, R ¹ as described below ⁵ and R ^{1 2}
Is a group further forming an aromatic ring.

[0029]

Embedded image Here, q has the same meaning as q in the formula (II).

The cyclic olefins represented by the above formula (I) or (II) are more specifically illustrated below.
As an example,

Embedded image (In the above general formula, the numbers 1 to 7 indicate the position numbers of carbon atoms) and a derivative obtained by substituting a hydrocarbon group for the compound. No.

As the substituted hydrocarbon group, 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- (ethyl Phenyl), 5-
(Isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl), and 5,6-diphenyl.

Further 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] -2-heptene derivatives such as hexahydroanthracene can be exemplified.

In addition, tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and other tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives, tricyclo [4.4.0.1
^2,5 ] -3-undecene, 10-methyltricyclo [4.4.0.1 ^2,5 ]
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as -3-undecene,

Embedded image In tetracyclo shown [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, and this hydrocarbon group include derivatives substituted.

The hydrocarbon groups 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-11,1
2-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), 5,6-diphenyl and the like are exemplified. be able to.

[0035] Furthermore, - tetracyclo such (cyclopentadiene acenaphthylene adduct) and adduct of cyclopentadiene [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives, pentacyclo [6.5.1.1 ^{3, 6.0 2,7} .0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5 .1
^9,12 .0 ^8,13] -3-pentadecene and its derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3 , 6.0} 2,7.0 ^9,14 ]-
4-hexadecene and its derivatives, hexacyclo [6.6.
1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene and its derivatives, heptacyclo ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3, ⁸ .0
^12,16 ] -5-Eicosene and its derivatives, heptacyclo
^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11,16] -4- eicosene and its derivatives, heptacyclo [8.8.0.1 ^2,9 .1 ^4,7. 1
^11,18 .0 ^3,8 .0 ^12,17] -5-heneicosene and its derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0
^3,8 .0 ^{12, 17} ] -5-docosene and its derivatives, nonacyclo
^{[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.

Specific examples of the above formula (I) or (II) which can be used in the present invention are as described above. More specific structures of these compounds are described in the application of the present applicant. And paragraphs [0032] to [0054] of JP-A No. 7-145213, and in the present invention, those exemplified in the above specification may be used as the cyclic olefin of the present invention. it can.

As a method for producing the cyclic olefin represented by the general formula (I) or (II) as described above, for example,
A Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure can be mentioned.

These cyclic olefins can be used alone or in combination of two or more. 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, JP-A-61-120816, 61
-115912, 61-115916, 61-271308, 61-2722
Nos. 16, 62-252406, 62-252407, etc., according to the method proposed by the present applicant, and by appropriately selecting conditions, it can be produced.

[A-1] α-olefin / cyclic olefin la
The random copolymer [A-1] α-olefin / cyclic olefin random copolymer contains 20 to 95 mol%, preferably 20 to 95 mol%, of structural units derived from α-olefin having 2 to 20 carbon atoms. In a quantity of 30 to 90 mol%, the structural unit derived from the cyclic olefin is usually 5 to 80 mol%, preferably 1 to 80 mol%.
It is contained in an amount of 0 to 70 mol%. The composition ratio of the α-olefin and the cyclic olefin is measured by ¹³ C-NMR.

Here, the α-olefin / cyclic olefin random copolymer [A-1] has 2 to 2 carbon atoms.
20 α-olefins will be described. The α-olefin may be linear or branched, and may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1-eicosene and the like, linear α-olefins having 2 to 20 carbon atoms; 3-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, etc. with 4 carbon atoms
To 20 branched α-olefins. Among these, linear α-olefins having 2 to 4 carbon atoms are preferred, and ethylene is particularly preferred. Such linear or branched α-olefins can be used alone or in combination of two or more.

In the [A-1] α-olefin / cyclic olefin random copolymer, the number of carbon atoms is 2
Structural units derived from α-20 olefins and structural units derived from cyclic olefins are randomly arranged and bonded to have a substantially linear 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, intrinsic viscosity [η]
Can be confirmed by completely dissolving this copolymer in decalin at 135 ° C.

In the [A-1] α-olefin / 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 (IV) ) Or (V).

[0043]

Embedded image In the formula (IV), n, m, q, R ^{1 to} R ¹⁸ and R ^a
And R ^b have the same meaning as in formula (I).

[0044]

Embedded image In formula (V), n, m, p, q and R ¹ to R ^{1 9} are the same meaning as in formula (II).

The [A-1] α-olefin / cyclic olefin random copolymer used in the present invention is, if necessary, derived from another copolymerizable monomer as long as the object of the present invention is not impaired. May be included.

Examples of such other monomers include olefins other than the above-mentioned α-olefins having 2 to 20 carbon atoms or cyclic olefins. Specifically, 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 can be mentioned. These other monomers can be used alone or in combination.

[A-1] In the α-olefin / cyclic olefin random copolymer, the constitutional unit derived from the above other monomer is usually 20 mol% or less, preferably 10 mol% or less. May be contained.

The [A-1] α-olefin / cyclic olefin random copolymer used in the present invention has 2 carbon atoms.
To α-20 and a cyclic olefin represented by formula (I) or (II) by the production method disclosed in the above-mentioned publication. Among these, this copolymerization is carried out in a hydrocarbon solvent, and a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent is used as a catalyst [A-
1] It is preferable to produce an α-olefin / cyclic olefin random copolymer.

In this copolymerization reaction, a solid group IV metallocene catalyst can be used. Where solid IV
The group metallocene-based catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organic aluminum oxy compound, and an organic aluminum compound optionally added. Here, the group IV transition metal is zirconium, titanium or hafnium, and these transition metals have a ligand containing at least one cyclopentadienyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group or 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. Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

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

[A-2] A ring-opened polymer of a cyclic olefin or
Is a copolymer [A-2] a ring-opening polymer of a cyclic olefin or a copolymer is a ring-opening polymer of a cyclic olefin represented by the formula (I) or (II); And / or a copolymer containing a ring-opening polymerization unit of a cyclic olefin represented by (II). In the case of a copolymer, two or more different cyclic olefins are used in combination.

In the ring-opened polymer or ring-opened copolymer of cyclic olefin, at least a part of the cyclic olefin represented by the above formula (I) or (II) is represented by the following formula (VI) or (VII). It is considered to constitute a repeating unit to be performed.

Embedded image In the formula (VI), n, m, q and R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as in the formula (I).

[0053]

Embedded image In formula (VII), n, m, p, q and R ¹ to R ^{1 9} are the same meaning as in formula (II).

Such a ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above-mentioned publication, for example, by subjecting a cyclic olefin represented by the above formula (I) to ring-opening polymerization. It can be produced by polymerization or copolymerization in the presence of a catalyst. As the ring-opening polymerization catalyst, ruthenium, rhodium, palladium, osmium,
A catalyst comprising a metal halide selected from indium or platinum, a nitrate or acetylacetone compound and a reducing agent, or a metal halide or acetylacetone compound selected from titanium, palladium, zirconium or molybdenum, and an organoaluminum compound Can be used.

[A-3] Hydrogen of ring-opened polymer or copolymer
The hydride of the ring-opening polymer or copolymer [A-3] used in the present invention is obtained by converting the ring-opening polymer or copolymer [A-2] obtained as described above into a conventionally known hydrogen-containing compound. It is obtained by hydrogenation in the presence of an added catalyst.

In this [A-3] hydride of the ring-opened polymer or copolymer, at least a part of the cyclic olefin represented by the formula (I) or (II) is represented by the following formula (VII)
It is considered to constitute the repeating unit represented by (I) or (IX).

[0057]

Embedded image In the formula (VIII), n, m, q and R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as in the formula (I).

[0058]

Embedded image N in formula (IX), m, p, q, R 1 ~R 1 9 formula (I
It has the same meaning as I).

[A-4] Graft Modified Product The graft modified product of the cyclic olefin resin is the above-mentioned [A-
1] α-olefin / cyclic olefin random copolymer,
[A-2] a ring-opened polymer or copolymer of a cyclic olefin,
Or [A-3] a graft modified product of a hydride of a ring-opening polymer or copolymer.

Examples of the modifier used herein include unsaturated carboxylic acids, and specific examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and crotonic acid. , Isocrotonic acid, endocis-bicyclo [2.2.1] hept-5-ene-
Unsaturated carboxylic acids such as 2,3-dicarboxylic acid (Nadic acid ^TM ), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic anhydrides, unsaturated carboxylic halides,
Examples thereof include unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and unsaturated carboxylic acid ester compounds.

More specifically, the derivatives of unsaturated carboxylic acids include maleic anhydride, citraconic anhydride, maleyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Of these, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. These modifiers can be used in combination of two or more.

Such a graft modified product of a cyclic olefin resin can be produced by blending a modifier with the cyclic olefin resin so as to obtain a desired modification ratio and graft-polymerizing the same. A modified product may be prepared by preparing a modified product, and then mixing the modified product with an unmodified cyclic olefin-based resin so as to have a desired modification rate.

In order to obtain a graft-modified product of a cyclic olefin resin from a cyclic olefin resin and a modifier, a conventionally known polymer modification method can be widely applied. For example, a graft-modified product is obtained by a method of adding a modifier to a molten cyclic olefin-based resin and performing graft polymerization (reaction), or a method of adding a modifier to a solvent solution of the cyclic olefin-based resin and performing a graft reaction. be able to.

Such a graft reaction is usually carried out at 60 to 3
It is performed at a temperature of 50 ° C. The graft reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

In the present invention, any one of the above-mentioned [A-1], [A-2], [A-3] and [A-4] is used alone as the cyclic olefin resin [A]. And these can be used in combination. Among them, α-olefin / cyclic olefin random copolymer [A-1], and further, ethylene / cyclic olefin random copolymer are preferably used. In particular, ethylene
Tetracyclododecene copolymer or ethylene-norbornene copolymer is preferred.

[B] Other Resin Component The other resin component [B] used in the present invention, which forms a resin composition together with the cyclic olefin resin [A], has a refractive index with the cyclic olefin resin [A]. Is a resin having a difference of 0.02 or more, preferably 0.03 or more. By adding another resin having a difference in refractive index of 0.02 or more, a transparent molded article can be made white (opaque) only with the cyclic olefin-based resin.

As the thermoplastic resin, polyolefin,
Polyamide, polyester, polyacetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polyacrylate, polymethacrylate, polycarbonate, polyphenylene oxide, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate and ethylene / (meth) acrylic acid Ester copolymers and the like can be mentioned.

Specifically, polyolefins include olefin homopolymers such as low-density polyethylene, high-density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and polymethylbutene; Copolymer, ethylene / 1-butene copolymer, ethylene represented by propylene / 1-butene copolymer, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, 1-dodecene, etc., random or block copolymers of α-olefins, ethylene-butadiene copolymer, ethylene-ethylidene norbornene copolymer Copolymer of α-olefin and conjugated diene or non-conjugated diene represented by union, ethylene-propylene-
Butadiene terpolymer, ethylene / propylene / dicyclopentadiene terpolymer, ethylene / propylene / ethylidene norbornene terpolymer, ethylene / propylene / 1,5-hexadiene terpolymer and the like. Or a copolymer of two or more α-olefins with a conjugated diene or a non-conjugated diene; polyamides such as aliphatics such as nylon-6, nylon-66, nylon-10, nylon-12 and nylon-46; Polyamides, aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines, etc .; Polyesters include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycaprolactone, polyhydroxybutyrate, etc .; polyacetals As a Examples include reformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde, and the like.

Examples of the polystyrene include styrene homopolymers, binary copolymers of styrene with acrylonitrile, methyl methacrylate, α-methylstyrene, etc., such as acrylonitrile-styrene copolymer;
As S, a structural unit derived from acrylonitrile is contained in an amount of 20 to 35 mol%, a structural unit derived from butadiene is contained in an amount of 20 to 30 mol%, and a structural unit derived from styrene is contained. Polyacrylate and polymethacrylate as polymethyl acrylate and polymethyl methacrylate (PMMA); polycarbonate as bis (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane and the like; as polyphenylene oxide, poly (2,6-dimethyl-1) , 4-phenylene oxide) and the like.

Examples of polyvinyl chloride include vinyl chloride homopolymer, copolymers of vinyl chloride and vinylidene chloride, acrylates, acrylonitrile, propylene, ethylene and the like;
A copolymer of vinyl chloride, acrylonitrile, (meth) acrylate, allyl ester, unsaturated ether, styrene and the like containing vinylidene chloride units in an amount of 85% or more; polyvinyl acetate includes vinyl acetate homopolymer,
Copolymers of vinyl acetate with ethylene and vinyl chloride;
Examples of the ethylene / (meth) acrylate copolymer include ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer; and ethylene / vinyl alcohol. Copolymers and the like.

The above thermoplastic resins can be used alone or in combination of two or more. Also,
These resins may have a crosslinked structure in the molecular chain. The crosslinking treatment of the polymer can be carried out by blending a polyfunctional monomer with the polymer and performing a known method such as ionizing radiation crosslinking or organic peroxide crosslinking.

Here, as the polyfunctional monomer, for example, a monomer having two or more ethylenically unsaturated bonds, particularly a vinyl bond, is preferably used. Specifically, divinylbenzene, tetramethylene diacrylate, ethylene glycol Examples thereof include dimethacrylate, 1,2,4-trivinylcyclohexane, and tetraallyloxyethane. The polyfunctional monomer is generally used in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight of the other resin component [B].

In ionizing radiation crosslinking, any of α-rays, β-rays, γ-rays, electron beams, X-rays and the like may be used as the ionizing radiation, and the irradiation dose is usually about 1 to 50 Mrad.

The organic peroxide crosslinking is a method in which a peroxide is added to another resin and then heated to a temperature equal to or higher than the decomposition temperature of the peroxide. -Butylperoxy) cyclohexane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t
-Butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,5,5
-Trimethylhexanoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide,
Examples thereof include 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, diisopropyl peroxydicarbonate, and di (2-ethylhexyl) peroxycarbonate.

The amount of the peroxide used is determined by the amount of the other resin component [B] 1
It is usually 0.01 to 5 parts by weight per 00 parts by weight. The degree of crosslinking is not particularly limited, and is appropriately selected according to the use of the synthetic paper.

When emulsion polymerization of an ethylenically unsaturated compound such as styrene, methyl (meth) acrylate or (meth) acrylic acid, a resin having a crosslinked structure can be obtained by coexisting the above-mentioned polyfunctional monomer. Obtainable.

Resin Composition The resin composition for forming the sheet or film-like molded article of the synthetic paper according to the present invention comprises [A] a cyclic olefin-based resin and [B] another resin as described above. The addition amount of the other resin component is preferably 1 to 100 parts by weight, more preferably 5 to 100 parts by weight based on 100 parts by weight of the cyclic olefin resin [A].
The amount is preferably from 70 to 70 parts by weight, particularly preferably from 10 to 40 parts by weight. Other resin components with a difference in refractive index of 0.02 or more
When [B] is added at this ratio, the molded article can be whitened while maintaining the excellent physical properties of the cyclic olefin-based resin.

The resin composition used in the present invention may contain a conventionally known weather-resistant stabilizer, heat-resistant stabilizer, antistatic agent, flame retardant, slip agent, anti-blocking agent, anti-fog, as long as the object of the invention is not impaired. Agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, and the like.

For example, the ultraviolet absorber of the weathering stabilizer to be added as an optional component includes benzophenone compounds, benzotriazole compounds, nickel compounds,
There are hindered amine compounds, specifically, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3'-t- Butyl-5'-butylphenyl) benzotriazole, nickel salt of bis (3,5-di-t-butyl-4-hydroxybenzoylphosphonic acid ethyl ester, bis (2,2 ', 6,6'-tetra Methyl-4-piperidine) sebacate and the like.

As the heat stabilizer to be added as an optional component, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane,
β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Phenolic antioxidants such as propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 1,2-hydroxystearate, glycerin monostearate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate And polyhydric alcohol fatty acid esters such as pentaerythritol tristearate, and the like, and also distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol-pentaerythritol diphosphite, bis
Phosphorus stabilizers such as (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite may be used. These may be blended alone or in combination. For example, tetrakis [methylene-3- (3.5-
Di-t-butyl-4-hydroxyphenyl) propionate]
Examples include a combination of methane, zinc stearate, and glycerin monostearate. These stabilizers can be used alone or in combination of two or more.

Further, the resin composition may contain an elastomer in an amount of usually not more than 10% by weight as long as the object of the present invention is not impaired. Specific examples of such an elastomer include EPR, EPDM, SBS, S
EBS, SIS, and SEPS.

As a method for producing such a resin composition, any known method can be employed. Specifically, for example, a cyclic olefin resin dry-blended in a predetermined ratio and another resin, a Banbury mixer, a roll mill,
Examples thereof include a method of obtaining pellets by melt-kneading with an extruder or the like, and a method of directly obtaining molded articles such as sheets and films from the above-described extruder.

Molded Article and Synthetic Paper The sheet or film-like molded article of the present invention can be produced by any known method. For example, the [A] cyclic olefin-based resin obtained as described above ,
[B] A method of molding a resin composition comprising another resin and, if necessary, other additives and the like by a method such as press molding, extrusion molding, inflation molding, injection molding, calendering, or the like.

Further, the sheet or film-like molded article of the present invention may be subjected to a stretching treatment. In producing a stretched sheet or film, usually, a raw sheet made of the resin composition is first formed. The raw sheet is obtained by a known method such as the above-mentioned molding method. Such a raw sheet usually has a thickness of 0.01 to
5 mm, preferably 0.2 to 2 mm. Next, the raw sheet is monoaxially or biaxially stretched to obtain a stretched sheet or film.

The stretching is usually performed by a uniaxial stretching device or a biaxial stretching device. As an example of the stretching conditions,
The stretching speed is, for example, 30 to 300 m / min, and the stretching ratio is, for example, 3 to 10 times for uniaxial stretching and 10 to 60 times for biaxial stretching. Biaxial stretching can be performed in the machine direction and the cross direction simultaneously or separately. The stretching temperature is, for example, 80 to 160 ° C. when stretching in the longitudinal direction, and is, for example, 130 to 170 ° C. when stretching in the transverse direction.

The thickness of the synthetic paper comprising the sheet or film-like molded article according to the present invention thus obtained is usually 10 μm to 2 mm, preferably 10 μm to 0.1 m.
m. Further, the total light transmittance is usually 50% or less,
Preferably it is 45% or less. In the present invention, the total light transmittance of the synthetic paper is a value measured according to ASTM D-1003. The haze of this synthetic paper is 80%
It is preferable that it is above.

Further, the synthetic paper according to the present invention may be subjected to a corona discharge treatment or the like, if necessary, so that the ink for printing or an ink jet printer can be easily attached.

When surface gloss is required for the synthetic paper of the present invention, a high gloss resin layer may be provided on the sheet or film. When matting is required, a matte resin layer may be provided on the sheet or film. When additional writing properties are required, it is preferable to provide a resin layer containing calcium carbonate, titanium oxide, or the like on this sheet or film. Various resins are used as described above in order to give various characteristics to synthetic paper, but in any case, those covered on both sides with those resins, those with only one side, those with a combination of them There is. As the lamination method, a co-extrusion method is preferable.

The synthetic paper according to the present invention has a tensile strength, a rigidity,
It is excellent in mechanical strength such as surface hardness, impact strength, cold resistance, etc., has sufficient opacity to maintain the appearance as paper, and has good tearability, folding properties, moisture proof properties, Base film for adhesive tape, wallpaper, notebook, copy paper, printing paper used for outdoor signage,
It is suitably used for applications such as food packaging.

[0091]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
The methods for measuring and evaluating various physical properties in this example are described below. (1) TMA (Softening Temperature) A quartz needle having a diameter of 1.0 mm is placed on a sheet and a load of 49 mm is applied.
The temperature at which the needle penetrated 0.635 mm into the sheet when the temperature was increased at a rate of 5 ° C./min by applying g was defined as TMA. (2) Tg (glass transition temperature) Tg was measured at a heating rate of 10 ° C./min using DSC. (3) MFR (melt flow rate) Measured based on ASTM D1238.

(4) Density: Measured according to ASTM D1505. (5) Refractive index Measured based on ASTM D542. (6) Haze Measured according to ASTM D1003. (7) Tearability It was evaluated according to the following criteria. ：: tears easily without resistance △: tears slightly with resistance ×: does not tear at all

(8) Return Angle (Bendability) A sample of 50 mm × 50 mm was cut out from the film of the example, and folded in two at the middle part of the film so as not to have streaks, and 100 g of 63 mm × 100 mm square was cut from the top. The metal plate was placed and kept at 23 ° C. for 1 minute to make a fold. Then, the angle when the fold of the film was opened to the maximum except the metal plate was measured. The smaller the value, the better the bendability. (9) Writability A line was written on the film with a ballpoint pen, and the writability was evaluated according to the following criteria. ○: Beautiful lines can be drawn △: Sometimes lines are faded ×: Lines cannot be drawn well

Example 1 Ethylene and tetracyclo [4.
4.0.1 referred to as ^2,5 .1 ^7,10] -3-random copolymer of dodecene (hereinafter ETCD, ethylene unit content: 75 mol%, TM
A: 90 ° C., Tg: 80 ° C., [η]: 0.65 dl / g, MF
R [260 ° C, load 2.16Kg]: 27g / 10min, refractive index 1.54)
To 100 parts by weight of pellets, a spherical cross-linked acrylic resin (average particle diameter 4 to 5 μm, refractive index 1.49, Nippon Shokubai
Ltd. EPOSTAR ^TM MA1004) were blended 10 parts by weight, to prepare a thick 50μm sheet at 30mmφ the T-die molding machine set to 230 ° C.. The haze, tearing property, bending property (return angle), and writing property were evaluated using this. Table 1 shows the results.

(Example 2) The same as Example 1 except that polystyrene having an MFR of 200 ° C, a load of 5 kg, 30 g / 10 min, and a refractive index of 1.59 was used in place of the spherical crosslinked acrylic resin of Example 1. Thus, a sheet having a thickness of 50 μm was obtained. Table 1 shows the results of the evaluation in the same manner as in Example 1. (Comparative Example 1) Instead of the spherical crosslinked acrylic resin of Example 1, a density of 0.968 g / cm ³ , MFR [190 ° C, load 2.16K
g] A sheet having a thickness of 50 μm was obtained in the same manner as in Example 1 except that high-density polyethylene having a refractive index of 1.54 was used at 5.2 g / 10 minutes. Table 1 shows the results of the evaluation in the same manner as in Example 1. (Comparative Example 2) The same operation as in Example 1 was performed using a composition obtained by mixing 10 parts by weight of the ETCD of Example 1 with 100 parts by weight of the high-density polyethylene of Comparative Example 1, and the thickness was 50 μm.
Sheet was obtained. Table 1 shows the results of the evaluation in the same manner as in Example 1.

[0096]

[Table 1]

[0097]

The synthetic paper according to the present invention has excellent mechanical properties such as tensile strength, rigidity, surface hardness, impact strength and cold resistance, as well as excellent water resistance, oil resistance and sufficient opacity. It has good tearability, bendability, and moisture resistance, so it can be used for thermal transfer image receiving paper, adhesive tape base film,
It is suitable for wallpaper, notebooks, copy paper, printing paper used for outdoor signage, and food packaging. Further, the synthetic paper of the present invention is opaque even if it does not contain inorganic solid particles and the like, and does not cause problems such as clogging of a screen during production.

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Claims (4)

[Claims] [A] The following [A-1], [A-2], [A-3] and [A-
4] The difference in refractive index between at least one cyclic olefin-based resin selected from the group consisting of
A synthetic paper comprising a sheet or a film-shaped molded product of a resin composition with at least two other resins; [A-1] an α-olefin having 2 to 20 carbon atoms and the following formula (I) ) Or a random copolymer of α-olefin and cyclic olefin obtained by copolymerizing a cyclic olefin represented by (II), (In the formula, n is 0 or 1, m is 0 or an integer of 1 or more, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{1 5} to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, and also monocyclic or polycyclic have a double bond good, and R ¹ is ⁵ and the R ^{1 6,} or R ^{1 7} and R ^{1 8} and in may form an alkylidene group.) [Chemical Formula 2] (Where p and q are 0 or an integer of 1 or more;
And n is 0, 1 or 2, each R ¹ to R ^{1 9} independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group,
Alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ and R ^{1 0} are attached,
The carbon atom to which R ^{1 3} or R ^{1 1} is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when the ^{n = m = 0, R 1} 5 and R ^{1 2} or R ^{1 5} and R ^{1 9} and may form a monocyclic or polycyclic aromatic ring bonded to each other. ), [A-2] a ring-opening polymer or copolymer of a cyclic olefin represented by the above formula (I) or (II), [A-3] a ring-opening polymer or copolymer of the above [A-2]. [A-4] a graft-modified product of the above [A-1], [A-2] or [A-3]. 2. The resin composition according to claim 1, wherein the other resin component [B] is contained in a proportion of 1 to 100 parts by weight based on 100 parts by weight of the cyclic olefin resin [A]. Item 2. The synthetic paper according to Item 1. 3. The synthetic paper according to claim 1, wherein the resin [B] is polymethyl methacrylate. 4. The sheet or film-like molded body,
The synthetic paper according to any one of claims 1 to 3, wherein the synthetic paper is obtained by stretching an extruded sheet or film.