JP2001026718A - Thermoplastic resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition excellent in transparency, low birefringence and the like, especially capable of stably maintaining the excellent transparency even in a changed environment, and useful for a molded product for an optical use, an optical recording media or the like by including a specific thermoplastic resin and a specified polyhydric alcohol in specific amounts. SOLUTION: This thermoplastic resin composition comprises (A) 100 pts.wt. thermoplastic resin having <=10%; haze and >=80% total light transmittance, measured based on ASTM D1003 by using a molded product having 3 mm thickness, and further having <=0.1% water absorption after 100 hr immersion in water at 230C, >=10 deg.C glass transition temperature and <=20 wt.% content of aromatic rings, and (B) 0.01-10 pts.wt. >=6C polyhydric alcohol having <=2,000 molecular weight, and 1.5-30 ratio of the number of carbons to the number of hydroxy groups in the same molecule. The component B is preferably an aliphatic polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent transparency, low water absorption, and being able to maintain transparency even under environmental changes. In particular, the present invention relates to a thermoplastic resin composition with little decrease in transparency in a high-temperature and high-humidity atmosphere, and its use.

[0002]

BACKGROUND OF THE INVENTION Generally, a transparent resin utilizes the property that light is easily transmitted therethrough so that the contents can be easily confirmed when made into a container or a packaging material, and that it is easy to carry and process. It has been used not only for industrial materials and general consumer materials, but also for pharmaceuticals, foods, laboratory equipment, optical applications, and the like. Specifically, it is suitably used as a transparent container for foods and pharmaceuticals, as well as lenses for optical devices such as spectacle lenses and pickup lenses, fθ lenses, and MO,
It is also used for optical recording media such as DVD and CD.

[0003] In such an application, the device is sometimes placed in an environment of a high temperature and high humidity atmosphere. For example, when used for containers of foods, pharmaceuticals, etc., washing treatment with hot water, steam, or the like is performed to sterilize the containers. Particularly, containers for pharmaceuticals and the like are usually subjected to steam sterilization. In addition, when used in optical products such as lenses for optical equipment and optical recording media, and food and pharmaceutical packaging products, the product may be placed in a harsh environment of high temperature and high humidity during the transportation of the product. . A small amount of water mixed in at that time
Agglomerates with a decrease in the ambient temperature, and generates minute cracks and voids considered to be caused by the aggregation. As a result, the appearance became cloudy, and the transparency of the product was sometimes impaired.

Heretofore, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like have been known as resins having excellent transparency. Polycarbonate is excellent in rigidity, heat resistance, heat aging resistance and impact resistance, but is inferior in chemical resistance, and when molded on optical substrates, etc., has large birefringence and low water absorption (water resistance) ) Is not enough. Polymethyl methacrylate has excellent mechanical properties,
There is a problem that the weather resistance is poor. Polyethylene terephthalate has excellent heat resistance and mechanical properties,
There is a problem that it is susceptible to hydrolysis due to being weak to strong acids or alkalis.

[0005] On the other hand, polyolefin resins are also known as resins having excellent transparency. In particular, polyolefin resins having a good balance between rigidity and transparency are used as polyolefin resins derived from bulky cyclic olefins. Coalescence has been proposed. For example, as a random copolymer of ethylene and this cyclic olefin, ethylene and 2,2
Copolymers with 3-dihydroxydicyclopentadiene (US Pat. No. 2,883,372) or copolymers of ethylene and 5-ethylidene norbornene have been proposed.

The present applicant has also studied such a cyclic olefin-based polymer, and found that an amorphous cyclic olefin-based polymer such as a copolymer of ethylene and a cyclic olefin has been converted to α-olefin (co) Various properties compared to polymers, such as electrical properties such as transparency, low birefringence, moisture proof (low water absorption), heat resistance, chemical resistance, solvent resistance, precision molding processability, dielectric properties, etc. It has been found that it has excellent mechanical properties, rigidity, etc.
708, JP-A-61-115916, JP-A-61-120816, etc.). For this reason, cyclic olefin polymers are considered to be used for a wide variety of applications. Particularly, their excellent transparency can be effectively used, for example, for optical applications, medical / pharmaceutical containers, and food containers. It is considered.

However, in the course of studying the use of such a cyclic olefin polymer, the cyclic olefin polymer becomes cloudy due to environmental changes, for example, when the atmosphere is changed from a high temperature and high humidity atmosphere to a normal temperature and normal humidity atmosphere. It has been found that this causes a problem that transparency or light transmittance may be reduced.

[0008] Poly-4-methyl-1-pentene resins are used in medical and pharmaceutical containers which are steam-sterilized because of their excellent heat resistance, rigidity and moisture resistance in addition to transparency. In addition, transparency may be reduced depending on the conditions of steam sterilization.

Such a decrease in transparency in a high-temperature, high-humidity atmosphere is a phenomenon that is likely to occur in a transparent resin having a low water absorption, and has been observed in styrene-based polymers, polycyclohexadiene, and the like.

Therefore, the appearance of a thermoplastic resin which can stably maintain excellent transparency without being reduced by environmental changes and can be suitably used for each of the above-mentioned applications is desired. I was

[0011]

DISCLOSURE OF THE INVENTION The present invention provides transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance,
Thermoplastic resin composition that has excellent dielectric properties, various mechanical properties, precision moldability, moisture resistance (low water absorption), etc., and especially can stably maintain excellent transparency even under environmental changes and uses thereof It is intended to provide.

[0012]

Means for Solving the Problems The thermoplastic resin composition according to the present invention comprises: [A] AS measured on a molded product having a thickness of 3 mm.
The haze according to TM D1003 is 10% or less, the total light transmittance is 80% or more, the water absorption in immersion in water at 23 ° C for 100 hours is 0.1% or less, the glass transition temperature is 10 ° C or more, and the aromatic ring is A thermoplastic resin having a content of 20% by weight or less and [B] a molecular weight of 2000 or less and a ratio of the number of carbon atoms to the number of hydroxyl groups in the same molecule of 1.
5 to 30 polyhydric alcohols having 6 or more carbon atoms (the polyhydric alcohol may contain an ether bond, a thioether bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group in the molecule) The thermoplastic resin [A] 10
0 parts by weight of the polyhydric alcohol [B] is 0.0%
It is characterized in that it is contained at a ratio of 1 to 10 parts by weight.

The thermoplastic resin [A] includes (a)
A cyclic olefin polymer selected from the group consisting of the following [A-1], [A-2], [A-3] and [A-4]; (b) a polycyclohexane resin; and (c) 4- It is preferably at least one selected from methyl-1-pentene polymers.

[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,

[0015]

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

[0016]

Embedded image (In the above formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹
Each independently hydrogen atom ^9, 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, R ^{1 3} or with the carbon atom to which 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, and R ^{1 5} 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].

Further, the thermoplastic resin composition according to the present invention comprises: [A] at least one thermoplastic resin selected from the following resins (a) to (c); , [A
-2], a cyclic olefin polymer selected from the group consisting of [A-3] and [A-4], (b) a polycyclohexane resin, and (c) a 4-methyl-1-pentene polymer,
[B] a polyhydric alcohol having a molecular weight of 2000 or less and a carbon number of 6 or more in which the ratio of the number of carbon atoms to the number of hydroxyl groups in the same molecule is 1.5 to 30 (the polyhydric alcohol is
The molecule may contain an ether bond, a thioether bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ), Wherein the polyhydric alcohol [B] is contained in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin [A].

[A-1] α-olefin / cycloolefin random obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms with a cyclic olefin represented by the above formula (I) or (II) A copolymer, [A-2] a ring-opening polymer or copolymer of the cyclic olefin represented by the formula (I) or (II), [A-3] a ring-opening polymer of the above [A-2] or Hydride of the copolymer, and [A-4] [A-1], [A-2] or [A-
3] The graft modified product.

Preferably, the polyhydric alcohol has at least one hydroxyl group in the molecule bonded to a primary carbon atom.

According to the present invention, the thermoplastic resin composition is preferably used as a plastic lens, container, transparent sheet or transparent board made of the thermoplastic resin composition.
An optical recording medium is provided.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition according to the present invention comprises a thermoplastic resin having excellent transparency and low water absorption, and a specific polyhydric alcohol. First, the thermoplastic resin will be described.

Thermoplastic resin [A] The thermoplastic resin [A] used in the present invention is mainly composed of carbon atoms and hydrogen atoms, and its transparency conforms to ASTM D1003 measured on a molded product having a thickness of 3 mm. Is preferably 10% or less, more preferably 5% or less, and the total light transmittance is usually 80% or more, preferably 85% or more, and is measured by immersing in 23 ° C. water for 100 hours. It is a resin having a low water absorption of preferably 0.1% or less.

The glass transition temperature (Tg) measured by DSC (differential scanning calorimeter) is preferably 10 ° C. or more, and the content of aromatic rings in the molecules constituting the resin is 20% by weight. % Or less is preferable.

Examples of such a thermoplastic resin include a cyclic olefin-based polymer, a poly-4-methyl-1-pentene-based resin, a polycyclohexane-based resin and the like, as well as the aforementioned transparency, glass transition temperature, and the like. A thermoplastic resin having an aromatic ring content, which has a hydroxyl group, an ester group, a carbonyl group, a hydrophilic group such as an amide group as a functional group in a basic skeleton structure composed of carbon atoms and hydrogen atoms, and has a functional group When the content of the group is low and the water absorption of the resin falls within the above range, such a resin is also included. Examples of such a resin include a resin obtained by modifying a cyclic olefin polymer with an acid anhydride represented by maleic acid.

Among these, (a) [A-1] described later,
A cyclic olefin polymer selected from the group consisting of [A-2], [A-3] and [A-4], (b) a polycyclohexane resin, and (c) a 4-methyl-1-pentene polymer It is preferably at least one selected from coalescence.

In the present invention, as the thermoplastic resin [A], (a) the following [A-1], [A-2], [A-3] and [A-3] without being restricted by the above physical property values. A-4], at least one selected from the group consisting of cyclic olefin polymers, (b) polycyclohexane resins, and (c) 4-methyl-1-pentene polymers. Hereinafter, each resin will be specifically described.

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

Here, the cyclic olefin represented by the formula (I) or (II) constituting the cyclic olefin polymer (a) will be described. The cyclic olefin used in the present invention is represented by the following formula (I) or (II).

[0030]

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 bond between R ^a and R ^b is lost, and the carbon atoms on both sides are bonded 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 have their hydrogen atoms replaced by halogen atoms.

[0034] In still above formula ^{(I), R 1 5 ~R} 18
May be bonded to each other (together with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed may have a double bond. Here, specific examples of the formed monocyclic or polycyclic ring are shown below.

Embedded image

In the above examples, the carbon atoms numbered 1 or 2 are each represented by R ¹⁵ (R
¹⁶ ) or a carbon atom to which R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0036]

Embedded image

In the above formula (II), p and q are 0 or 1.
Where m and n are 0, 1 or 2. The R ¹ to R ^{1 9} are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group. The halogen atom has the same meaning as the halogen atom in the formula (I).

As the hydrocarbon group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group is independently used. Is mentioned. 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 as the aromatic hydrocarbon group, an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenylethyl group are exemplified.

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

[0040] 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.

[0041] Further, 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.

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 (Also referred to as norbornene. In the above formula, the numbers 1 to 7 represent the position numbers of carbon atoms) and derivatives obtained by substituting the compound with a hydrocarbon group. .

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.

Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a -
Bicyclo [2.2.1] -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 shown as tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (in subsequent simply in. The formula of tetracyclododecene, 1 to 12 numbers indicate the position numbers of carbon.),
And derivatives thereof substituted with a hydrocarbon group.

The hydrocarbon group for the substituent includes 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl,
8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-
Dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl-9-
Methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-
Trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-
11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9-methyl, 8-ethylidene-9-ethyl,
8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8
-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9- Ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl
-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8-
(Biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8-
(Anthracenyl) and 5,6-diphenyl.

Further derivatives include adducts of (cyclopentadiene-acenaphthylene adduct) with cyclopentadiene.

Further, tetracyclo [4.4.0.1^2,5.1^7,10] -3
-Dodecene derivative, 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
Derivative, pentacyclo [6.5.1.1^{Three , 6}.0^{Two , 7}.0^{9 ,13}] -4,10-
Pentadecadiene compound, pentacyclo [8.4.0.1^2,5.1
^9,12.0^8,13] -3-Hexadecene and its derivatives, penta
Cyclo [6.6.1.1^3,6.0^2,7.0^{9, 14}] -4-hexadecene and
Its derivative, 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-Eikosen
And its derivatives, heptacyclo [8.7.0.1^3,6.1^{1 0,17}.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]-Five
-Hen eicosene 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-pentacocene and
And its derivatives, nonacyclo [10.10.1.1^{Five , 8}.1^{1 Four , 2 1}.1^{1 6 , 1
9}.0^{2,1 1}.0^{Four , 9}.0^{1 Three , 2 Two}.0^{1 Five , 20}] -6-Hexacocene and its
And the like.

Specific examples of the cyclic olefin represented by the formula (I) or (II) which can be used in the present invention are as described above. More specific structures of these compounds are as follows. These are shown in paragraphs [0032] to [0054] of JP-A-7-1445213. In the present invention, those exemplified in the specification can be used as cyclic olefins.

Examples of the method for producing the cyclic olefin represented by the above formula (I) or (II) include a Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure. I can do it.

These cyclic olefins can be used alone or in combination of two or more.

The cyclic olefin polymer (a) used in the present invention can be prepared by using the cyclic olefin represented by the above formula (I) or (II), for example, as described in JP-A-60-168.
No. 708, No. 61-120816, No. 61-115912, No. 61-115916
No. 61-271308, No. 61-272216, No. 62-252406, and No. 62-252407, and can be produced by appropriately selecting conditions according to the methods proposed in the publications.

Α-olefin having 2 to 20 carbon atoms
The cyclic olefin random copolymer [A-1] has a constitutional unit derived from a cyclic olefin in an amount of usually from 5 to 95 mol%, preferably from 20 to 80 mol%, of a structural unit derived from an α-olefin. The unit is usually 5 to 95 mol%,
Preferably, it is contained in an amount of 20 to 80 mol%. The composition ratio of α-olefin and cyclic olefin is ¹³ C
-Measured by 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 α-olefin / cyclic olefin random copolymer [A-1], the constitutional unit derived from the α-olefin having 2 to 20 carbon atoms and the constitution derived from the cyclic olefin as described above. The units are randomly arranged and combined to have a substantially linear structure. The fact that this copolymer is substantially linear and does not have a substantially gel-like cross-linked structure means that when this copolymer is dissolved in an organic solvent, the solution contains an insoluble component. You can confirm by not having. For example, when the intrinsic viscosity [η] is measured, it can be confirmed by completely dissolving this copolymer in decalin at 135 ° C.

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

[0057]

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

[0058]

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

The α-olefin used in the present invention
If necessary, the cyclic olefin random copolymer [A-1] may have a structural unit derived from another copolymerizable monomer as long as the object of the present invention is not impaired.

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.

When the α-olefin / cyclic olefin random copolymer [A-1] contains a structural unit derived from another monomer as described above, it is usually 2 units.
The amount is preferably 0 mol% or less, more preferably 10 mol% or less.

The α-olefin / cyclic olefin random copolymer [A-1] used in the present invention is a mixture of an α-olefin having 2 to 20 carbon atoms and a cyclic compound represented by the formula (I) or (II). It can be produced by using the olefin and the production method disclosed in the above publication. Among these, a production method in which the copolymerization reaction is carried out in a hydrocarbon solvent and a catalyst formed from a vanadium compound and an organic aluminum compound soluble in the hydrocarbon solvent is preferable.

In this copolymerization reaction, a solid metallocene catalyst of Group IV of the periodic table may be used. Here, the solid group IV metallocene catalyst of the periodic table is a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organic aluminum oxy compound, and an organic aluminum compound optionally blended. Catalyst. Here, examples of the transition metal of Group IV of the periodic table include zirconium, titanium and hafnium, and these transition metals are catalysts having 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 polyolefins can be used. Examples of such a solid group IV metallocene catalyst of the periodic table include those described in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112. Can be used.

The ring-opened polymer or copolymer [A-2] of the cyclic olefin may be a ring-opened polymer of the cyclic olefin represented by the above formula (I) or (II) or a compound of the above formula (I) and / or 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 [A-2] of the cyclic olefin, at least a part of the cyclic olefin represented by the above formula (I) or (II) has the following formula (V) or It is considered to constitute the repeating unit represented by (VI).

[0067]

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

[0068]

Embedded image In the above formula (VI), n, m, p, q and R ^{1 to} R ^1
9 has 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, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the formula (II) in the presence of a ring-opening polymerization catalyst. Examples of the ring-opening polymerization catalyst include ruthenium, rhodium, palladium, osmium, a metal halide selected from indium or platinum, a nitrate or acetylacetone compound, and a catalyst comprising a reducing agent, or titanium, palladium,
A catalyst comprising a metal halide selected from zirconium or molybdenum or an acetylacetone compound and an organoaluminum compound can be used.

Hydrogenated ring-opened polymer or copolymer [A-
3] is obtained by hydrogenating the ring-opened polymer or copolymer [A-2] obtained as described above in the presence of a conventionally known hydrogenation catalyst.

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

[0072]

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

[0073]

Embedded image In the above formula (VIII), n, m, p, q, R ^{1 to} R
^{1 9} has the same meaning as those in formula (II).

The graft-modified cyclic olefin polymer [A-4] may be the above-mentioned ethylene / cyclic olefin random copolymer [A-1], a cyclic olefin ring-opened polymer or a copolymer [A-2]. Or a graft modified product of a hydride [A-3] of a ring-opening polymer or copolymer.

Examples of the modifying agent 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-2,
Unsaturated carboxylic acids such as 3-dicarboxylic acid (nadic ^TM), further derivatives such as unsaturated carboxylic acid anhydrides of these unsaturated carboxylic acids, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, Examples thereof include unsaturated carboxylic acid ester compounds.

The derivatives of unsaturated carboxylic acids include more specifically 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 ^TM 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 polymer can be produced by blending a modifier with the cyclic olefin polymer so as to obtain a desired modification ratio and graft-polymerizing the compound. The modified product may be prepared by preparing a modified product having a desired modification ratio, and then mixing the modified product with an unmodified cyclic olefin-based polymer so as to obtain a desired modification ratio.

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

The grafting 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, as the cyclic olefin polymer (a), [A-1], [A-2], [A-
Any of [3] and [A-4] can be used alone, or two or more of the same group or two or more different groups can be used in combination.

The above-mentioned cyclic olefin polymer (a) is
The glass transition temperature (Tg) measured by DSC is 60-23.
0 ° C., more preferably 70 to 210 ° C.
It is preferable that

The cyclic olefin polymer (a) is
It is amorphous or low crystalline, and the degree of crystallinity measured by X-ray diffraction is usually 20% or less, preferably 10% or less, and more preferably 2% or less.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is preferably 0.01 to 20 dl / g,
It is more preferably 0.05 to 10 dl / g, and still more preferably 0.08 to 5 dl / g.

Temperature 260 according to ASTM D1238
° C, melt flow index (MF) measured at a load of 2.16 kg
R) is generally 0.1 to 200 g / 10 min, preferably 1 to 100 g / 10 min, and more preferably 3 to 60 g.
/ 10 minutes.

The softening point is usually 30 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. as the softening point (TMA) measured by a thermal mechanical analyzer.
As described above, the temperature is more preferably 90 to 250 ° C, particularly preferably 100 to 200 ° C.

When the molecule constituting the resin contains an aromatic ring, the content of the aromatic ring is preferably 20% by weight or less, more preferably 15% by weight or less.

Among the above-mentioned cyclic olefin polymers (a), α-olefin / cyclic olefin random copolymer [A-1], ring-opened polymer or copolymer of cyclic olefin [A-2], And a ring-opening polymer or copolymer [A-2] selected from the group consisting of hydrides [A-3] having a softening point (TM
A) is 80 ° C. or higher and the intrinsic viscosity [η] is 0.0
Those having 5 to 10 dl / g are preferred.

Further, α-olefin / cyclic olefin random copolymer [A-1] is preferable, and ethylene / tetracyclododecene copolymer or ethylene / norbornene copolymer is particularly preferable.

Next, the polycyclohexane resin (b) will be described. The polycyclohexane-based resin (b) used in the present invention includes poly (1,3-cyclohexadiene) polymerized with alkyl lithium and amine as initiators.
Polycyclohexane obtained by hydrogenating the double bond in the polymer chain of cyclohexadiene, hydrogenated copolymer of 1,3-cyclohexadiene and α-olefin or styrene, and further impact Hydrogenated butadiene as a soft segment in order to improve strength, styrene or α
Hydrogenated copolymers of aromatic vinyl compounds such as -alkylstyrene and α-olefins having 3 to 20 carbon atoms, and hydrogenated benzene rings of styrene-based polymers obtained by polymerizing styrene or α-alkylstyrene And polycyclohexylethylene obtained by the addition. Here, the hydrogenation rate of the aromatic ring is preferably 60% or more, and more preferably 90% or more.

The polycyclohexylethylene suitably used in the present invention has a ratio (Mw / Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in terms of polystyrene molecular weight of usually 6 or less, preferably 5 or less. , More preferably 3 or less, still more preferably 2.5 or less. The weight average molecular weight is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 20,000 to 700,000, still more preferably in the range of 50,000 to 500,000, and especially in the range of 70,000 to 300,000. Excellent and preferred.

The glass transition temperature is usually 50 to 300 ° C.,
Preferably from 60 to 280C, more preferably from 70 to 25.
0 ° C. range and the crystallinity is 0-20%, preferably
It is 0 to 10%, more preferably 0 to 5%. The density is
0.80 to 1.50 g / cm ^Three, Preferably 0.85-
1.0g / cm^Three, More preferably 0.90 to 0.95
g / cm^ThreeIt is.

Polycyclohexylethylene can be obtained by hydrogenating the aromatic ring of polystyrene or the like by a known method. As the hydrogenation method, a conventionally known method can be applied, and examples thereof include methods described in JP-A-7-247321 and US Pat. No. 5,612,422. The hydrogenation rate of the aromatic ring is preferably 60% or more, and more preferably 90% or more.

Next, a 4-methyl-1-pentene polymer (c)
Will be described. The 4-methyl-1-pentene polymer (c) used in the present invention is a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and another α-olefin. Coalescing, for example ethylene, propylene, 1-
It is a copolymer with an α-olefin having 2 to 20 carbon atoms such as butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, and 1-octadecene. Among them, 50 mol% of 4-methyl-1-pentene homopolymer or 4-methyl-1-pentene structural unit is preferred from the viewpoint of heat resistance during steam sterilization.
As described above, it is preferable to use a copolymer of 4-methyl-1-pentene containing at least 70 mol% and the above-mentioned α-olefin.

M of 4-methyl-1-pentene polymer (c)
FR was measured at 260 ° C under a load of 5 according to ASTM D1238.
The value measured in kg is preferably in the range of 1 to 400 g / 10 minutes, and more preferably in the range of 10 to 300 g / 10 minutes.

Among the above thermoplastic resins [A], they are selected from the group consisting of [A-1], [A-2] and [A-3], and have a softening point (TMA) of 80 ° C. or more. Preferably, it is a cyclic olefin polymer having an intrinsic viscosity [η] of 0.05 to 10 dl / g.

In the present invention, a resin composition in which another resin is further blended with the above-mentioned thermoplastic resin, if necessary, can be used. Other resins are added within a range that does not impair the purpose of the present invention.

Here, other resins that can be added to the thermoplastic resin are exemplified below. (1) Polymers derived from hydrocarbons having one or two unsaturated bonds Specifically, for example, polyethylene, polypropylene, polymethylbutene-1, poly4-methylpentene-1, polybutene-1 and Examples include polyolefins such as polystyrene. These polyolefins may have a crosslinked structure. (2) Halogen-containing vinyl polymer Specific examples include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, and chlorinated rubber.

(3) Polymers derived from α, β-unsaturated acids and derivatives thereof Specifically, polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, or copolymers with the monomers constituting the above polymers Polymers such as acrylonitrile / butadiene / styrene copolymer, acrylonitrile / styrene copolymer, acrylonitrile / styrene
Styrene / acrylate copolymers and the like can be mentioned.

(4) Polymers Derived from Unsaturated Alcohols and Amines, or Acyl Derivatives or Acetals of Unsaturated Alcohols Specifically, polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, polyvinyl benzoate, polymaleic acid Examples thereof include vinyl, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, and a copolymer with a monomer constituting the polymer, for example, an ethylene / vinyl acetate copolymer.

(5) Polymer Derived from Epoxide Specific examples thereof include a polymer derived from polyethylene oxide or bisglycidyl ether. (6) Polyacetal Specifically, polyoxymethylene, polyoxyethylene,
Examples of the comonomer include polyoxymethylene containing ethylene oxide. (7) Polyphenylene oxide (8) Polycarbonate (9) Polysulfone (10) Polyurethane and urea resin

(11) Diamine and dicarboxylic acid and / or
Or polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams, specifically nylon 6, nylon 66, nylon 11,
Nylon 12 and the like. (12) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or corresponding lactones Specific examples include polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol / cyclohexane terephthalate, and the like.

(13) Polymer having a crosslinked structure derived from aldehyde and phenol, urea or melamine Specific examples include phenol / formaldehyde resin, urea / formaldehyde resin, melamine / formaldehyde resin and the like. (14) Alkyd resin Specific examples include glycerin / phthalic acid resin.

(15) Unsaturated polyester resins and halogen-containing modified resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using a vinyl compound as a crosslinking agent. (16) Natural Polymers Specific examples include cellulose, rubber, protein, and derivatives thereof such as cellulose acetate, cellulose propionate, and cellulose ether.

(17) Soft Polymer For example, a soft polymer containing a cyclic olefin component, an α-olefin copolymer, an α-olefin / diene copolymer, an aromatic vinyl hydrocarbon / conjugated diene soft copolymer Examples include a polymer, a soft polymer or a copolymer comprising isobutylene or isobutylene / conjugated diene.

As a method of mixing the thermoplastic resin used in the present invention with other resin components, additives and the like, a method known per se can be applied. For example, there is a method of simultaneously mixing the components.

Polyhydric alcohol [B] The polyhydric alcohol [B] used in the present invention has a molecular weight of 20.
The ratio of the number of carbon atoms to the number of hydroxyl groups in the same molecule is 1.5 to 30, preferably 3 to 20, particularly preferably 6 to 20, and 6 or more. As long as the ratio and the number of carbon atoms are within the ranges, the compatibility with the thermoplastic resin [A] is good, and there is no adverse effect on transparency due to foaming during melt kneading. A preferred range of carbon number is 6 to 100, and more preferably 6 to 60.
It is.

The polyhydric alcohol [B] is preferably one in which at least one hydroxyl group in the molecule is bonded to a primary carbon atom.

The polyhydric alcohol [B] of the present invention includes those having an ether bond, a thioether bond, an alicyclic hydrocarbon group or an aromatic hydrocarbon group in the molecule.
Preferred are aliphatic polyhydric alcohols. Further, those having an ester group are not included.

Specific examples of polyhydric alcohols include 3,7,1
1,15-tetramethyl-1,2,3-trihydroxyhexadecane, dihydroxyoctane, trihydroxyoctane,
Examples thereof include tetrahydroxyoctane, dihydroxynonane, trihydroxynonane, tetrahydroxynonane, pentahydroxynonane, hexahydroxynonane, dihydroxytriacontan, trihydroxytriacontan, and eicosahydroxytriacontan. Among these polyhydric alcohols, 3,7, described in Examples
11,15-Tetramethyl-1,2,3-trihydroxyhexadecane is preferred.

Thermoplastic Resin Composition The thermoplastic resin composition according to the present invention comprises the above-mentioned thermoplastic resin [A] and polyhydric alcohol [B], and is based on 100 parts by weight of the thermoplastic resin [A]. , 0.01 to 10 parts by weight, preferably 0.05 to 1 part by weight of polyhydric alcohol [B].
0 parts by weight, more preferably 0.05 to 7 parts by weight, even more preferably 0.1 to 5 parts by weight. When the content is within this range, a decrease in transparency due to environmental changes can be reduced without changing the transparency or the water absorption of the thermoplastic resin [A].

The thermoplastic resin composition according to the present invention has transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, various mechanical properties, and precision. Excels in moldability and moisture resistance (low water absorption). Particularly, the thermoplastic resin [A] and the polyhydric alcohol [B] having a specific structure
And a specific ratio, so that it does not affect the transparency or water absorption of the thermoplastic resin, providing excellent transparency even when the environment changes from a high-temperature, high-humidity atmosphere to a normal temperature, normal humidity atmosphere. Can be held.

The above-mentioned thermoplastic resin composition may contain any other components together with the thermoplastic resin [A] and the polyhydric alcohol [B] as long as the object of the present invention is not impaired. Well, for example, stabilizers such as weather stabilizers and heat stabilizers, crosslinking agents, crosslinking assistants, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, mineral oil softening Agents, petroleum resins, natural oils, synthetic oils, waxes, organic or inorganic fillers and the like.

Examples of the ultraviolet absorbers of the weathering stabilizer incorporated as such optional components include benzophenone-based compounds, benzotriazole-based compounds, nickel-based compounds and hindered amine-based compounds.
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 '-Tetramethyl-4-piperidine) sebacate and the like.

Examples of stabilizers contained as optional components include 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′-oxazamide bis [ethyl-3- (3, Phenolic antioxidants such as 5-di-t-butyl-4-hydroxyphenyl) propionate; and fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 1,2-hydroxystearate. These can be used in combination. For example, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is used in combination with zinc stearate or calcium stearate. Can be.

Further, as a stabilizer, for example, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol-pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol-A-pentaerythritol diphosphite, tris (2,4-di-
(t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphite, bis (2,
Phosphorus stabilizers such as 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite can also be used. These stabilizers can be used alone or in combination of two or more.

Examples of the organic or inorganic filler include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, Calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica,
Examples include asbestos, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, and the like.

As the method for producing the thermoplastic resin composition of the present invention, any known method can be employed. In particular,
For example, when using an extruder to melt a thermoplastic resin, or when the already melted resin passes through the extruder, a predetermined amount of polyhydric alcohol is injected into the extruder, a method of kneading to obtain pellets, Alternatively, a method of directly obtaining a sheet, a film, a blow-molded product or the like from the extruder can be used.

As a method not using an extruder, there is a method of obtaining a composition by dissolving a thermoplastic resin in a solvent, adding a predetermined amount of a polyhydric alcohol, stirring the mixture, and volatilizing the solvent. Also, as long as it does not hinder the production of the resin, it may be added at a stage before passing through the extruder. Further, a method of impregnating a thermoplastic resin powder or pellet in a polyhydric alcohol by applying temperature and pressure may be used. In addition, it is also possible to use these methods together.

When the thermoplastic resin composition obtained in this manner is used, while using a thermoplastic resin having a low water absorption,
By containing the polyhydric alcohol according to the present invention, it is possible to obtain a molded article which is excellent in transparency, steam sterilization or the like, and hardly causes a decrease in transparency under a high-temperature and high-humidity atmosphere, and does not cause cloudiness in appearance. Can be.

As a method for producing the thermoplastic resin molded article of the present invention, any known method can be employed. For example, a thermoplastic resin and a polyhydric alcohol obtained as described above,
If necessary, extrusion molding, injection molding, injection compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calender molding Various moldings such as a lens, a container, a tray, a sheet, and a film can be obtained by such molding methods.

The molded article made of the thermoplastic resin composition according to the present invention has transparency, low birefringence, heat resistance, heat aging resistance,
It is excellent in mechanical properties such as chemical resistance, solvent resistance, dielectric properties, rigidity, etc., precision moldability, and moisture resistance, so it can be used for plastic lenses such as spherical lenses, aspheric lenses, Fresnel lenses, etc. , Prism, light guide plate, reflection plate, optical fiber and other optical components; CD, MD, DV
Optical recording media such as D, MO, PD, etc .; Transparent board; Test tubes, vials, ampules, tablet bottles, prefilled syringes, disposable syringes, analytical cells, infusion bags, blood collection tubes, etc., medical and medical containers; wide-mouth containers;
Daily miscellaneous goods / food containers such as shampoo containers, coffee containers, seasoning containers, beverage containers, etc .; and transparent sheets. Among these, plastic lenses, containers, transparent sheets and boards, and optical recording media are particularly preferred.

[0123]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

A method for measuring physical properties in the present example will be described below. (1) Softening point (TMA) Using DuPont Thermo Mechanical Analyzer,
It was measured by the thermal deformation behavior of a sheet having a thickness of 1 mm. A quartz needle with a load of 49 g was placed on the sheet, and the temperature was raised at a rate of 5 ° C./min. The temperature at which the needle penetrated 0.635 mm into the sheet was defined as the softening point (TMA). (2) Light transmittance and haze (HAZE) Measured based on ASTM D1003. The sample contains
A 130 mm × 120 mm × 3 mm (thickness) square plate molded by an injection molding machine (IS-50 manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 270 ° C. and a mold temperature of 115 ° C. was used.

(3) Water Absorption A square plate formed in the same manner as in (2) was dried under reduced pressure at 80 ° C. and 1 torr for 24 hours, and then immersed in deionized water at 23 ° C. for 100 hours. Then, the water was pulled up from the water and wiped off the water adhered to the surface of the square plate. Then, 2 g of the water was cut out, and the water content was measured by the Karl Fischer method to determine the water absorption (% by weight).
I asked. (4) Melt flow index (MFR) Temperature according to ASTM D1238: 260 ° C or 200 ° C
° C and a load of 2.16 kg or 5 kg.

(5) Glass transition temperature (Tg) Measured at a heating rate of 10 ° C./min using DSC-20 manufactured by SEIKO Electronic Industries. (6) Crystallinity It was measured by the X-ray diffraction method. (7) Aromatic ring content Measured by H ¹ -NMR and C ¹³ -NMR.

(Example 1) As a thermoplastic resin [A],
Total light transmittance 90%, haze 3%, water absorption 0.01% or less, softening point (TMA) 150 ° C, intrinsic viscosity [η] 0.6d
l / g, a random copolymer 100 of ethylene and tetracyclododecene having a glass transition temperature (Tg) of 138 ° C.
3,7,11,15-Tetramethyl-1,2,3-trihydroxyhexadecane (molecular weight: 331, carbon number: 20, C number / OH group number: 6.7) by weight as polyhydric alcohol [B] 2
Parts by weight, and 0.6 parts by weight of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane as another additive. Twin screw extruder (T
EX-44) and melt-kneaded to obtain a thermoplastic resin composition.

The obtained thermoplastic resin composition was 3 m thick using an injection molding machine (IS-55EPN manufactured by Toshiba Machine Co., Ltd.).
m was injection molded into a square plate. 80 ° C, 90% R
After leaving for 48 hours under high temperature and high humidity of H (relative humidity),
It was taken out at normal temperature and normal humidity. Change in spectral light transmittance (ΔTr (600 nm)) obtained by subtracting spectral light transmittance at a wavelength of 600 nm after treatment from spectral light transmittance at a wavelength of 600 nm before the treatment and haze obtained by subtracting haze before the treatment from haze after the treatment. The change in transparency (ΔHAZE) was used to evaluate the transparency. Table 1 shows the results.

(Example 2) As polyhydric alcohol [B]
3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetra instead of 3,7,11,15-tetramethyl-1,2,3-trihydroxyhexadecane Oxaspiro [5.5] undecane (molecular weight 304, carbon number = 15, C number / OH group number = 7.
Except for using 5), a square plate was formed in the same manner as in Example 1 and the transparency was evaluated. Table 1 shows the results.

Comparative Example 1 A square plate was formed in the same manner as in Example 1 except that no polyhydric alcohol was added, and the transparency was evaluated. Table 1 shows the results. (Comparative Example 2) Using pentaerythritol (molecular weight 136, carbon number = 5, C number / OH group number = 1.25) as polyhydric alcohol [B], melt-kneading in the same manner as in Example 1, and a transparent resin composition However, foaming was impossible and molding was not possible.

(Example 3) The thickness of 3 m obtained in Example 1
After visually observing the appearance of the injection molded square plate of m
The solution was subjected to steam sterilization at 20 ° C. for 20 minutes. Transparency was evaluated by the change in spectral light transmittance before and after the treatment (ΔTr (600 nm)) and the change in haze (ΔHAZE). Table 1 shows the results. Example 4 The appearance of the injection-molded square plate having a thickness of 3 mm obtained in Example 2 was visually observed, and the same treatment as in Example 3 was performed. Change in spectral light transmittance before and after processing (ΔTr (600
nm)) and the change in haze (ΔHAZE) was used to evaluate the transparency. Table 1 shows the results.

Example 5 As a thermoplastic resin [A],
Poly 4-methyl-1-pentene having a total light transmittance of 94%, a haze of 3% and a water absorption of 0.01% or less (TP, manufactured by Mitsui Chemicals, Inc.)
X RT-18, MFR [260 ° C, load 5kg]: 23g / 10
And a glass transition temperature (Tg) of 24 ° C.) to obtain a thermoplastic resin composition in the same manner as in Example 1. The obtained thermoplastic resin composition was injected into an injection molding machine (I manufactured by Toshiba Machine Co., Ltd.).
(S-55EPN) and injection molded into a square plate having a thickness of 3 mm. After visually observing the external appearance of this square plate, 2 ° C. at 121 ° C.
Steam sterilization was performed for 0 minutes. Change in spectral light transmittance before and after treatment (ΔTr (600 nm)) and change in haze (ΔH
AZE) was used to evaluate the transparency. Table 1 shows the results.

Example 6 A thermoplastic resin [A] was prepared using poly-4-methyl-1-pentene having a total light transmittance of 94%, a haze of 3% and a water absorption of 0.01% or less (TPX, manufactured by Mitsui Chemicals, Inc.). R
T-18, MFR [260 ° C., load 5 kg]: 23 g / 10 minutes,
A transparent resin composition was obtained in the same manner as in Example 2, except that the glass transition temperature (Tg) was 24 ° C. The obtained transparent resin composition was evaluated in the same manner as in Example 5. Table 1 shows the results.

(Comparative Example 3) The transparency was evaluated in the same manner as in Example 3 except that no polyhydric alcohol was added. Table 1 shows the results. (Comparative Example 4) Transparency was evaluated in the same manner as in Example 5 except that no polyhydric alcohol was added. Table 1 shows the results.

(Example 7) As the thermoplastic resin [A],
Polystyrene having a total light transmittance of 89%, a haze of 2% and a water absorption of 0.05% (G590, MF manufactured by Nippon Polystyrene Co., Ltd.)
R [200 ° C., load 5 kg]: 3 g / 10 min) 100 g in cyclohexane solvent in the presence of Ni (acac) ₂ and triisobutylaluminum as catalysts, 100 ° C., 40 kg / cm ²
At room temperature for 2 hours (total light transmittance 91%, haze 3%, water absorption 0.01% or less, glass transition temperature (Tg) 146 ° C, aromatic ring content 2% by weight or less) ), 100 parts by weight of the transparent resin, 2 parts by weight of 3,7,11,15-tetramethyl-1,2,3-trihydroxyhexadecane are kneaded with a laboplast mill,
A pressed sheet of 30 mm × 30 mm × 3 mm (thickness) was formed at 280 ° C. This square plate was evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 5 Transparency was evaluated in the same manner as in Example 7 except that no polyhydric alcohol was added. Table 1 shows the results.

[0137]

[Table 1]

[0138]

The thermoplastic resin composition according to the present invention has transparency, low birefringence, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, various mechanical properties, precision molding. Moldability, moisture-proof (low water absorption), etc., and also can stably maintain excellent transparency especially due to environmental changes.
It is highly useful as various containers for medicine, medical treatment, food, etc., transparent sheets and boards, optical recording media such as CD, MD, DVD, MO, PD, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 65/00 C08L 65/00 G02B 1/04 G02B 1/04 G11B 7/24 526 G11B 7/24 526M

Claims (13)

[Claims] 1. [A] AS measured on a molded product having a thickness of 3 mm
The haze according to TM D1003 is 10% or less, the total light transmittance is 80% or more, the water absorption in immersion in water at 23 ° C for 100 hours is 0.1% or less, the glass transition temperature is 10 ° C or more, and the aromatic ring is A thermoplastic resin having a content of 20% by weight or less and [B] a molecular weight of 2000 or less and a ratio of the number of carbon atoms to the number of hydroxyl groups in the same molecule of 1.
5 to 30 polyhydric alcohols having 6 or more carbon atoms (the polyhydric alcohol may contain an ether bond, a thioether bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group in the molecule) The thermoplastic resin [A] 10
0 parts by weight of the polyhydric alcohol [B] is 0.0%
A thermoplastic resin composition containing 1 to 10 parts by weight. 2. The thermoplastic resin [A] is (a) a cyclic olefin selected from the group consisting of the following [A-1], [A-2], [A-3] and [A-4]. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is at least one selected from a polymer, (b) a polycyclohexane-based resin, and (c) a 4-methyl-1-pentene-based polymer; [A-1] α-olefin / cyclic olefin random copolymer obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms with a cyclic olefin 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, q is 0 or 1, and R ¹ to
R ^18, R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{1 5} to R ¹⁸
In may form a monocyclic or polycyclic bonded to each other, and may be monocyclic or polycyclic have a double bond, also an R ^{1 5} and R ^{1 6} or R, ^{1 7} and with a R ^{1 8} may form an alkylidene group. ), Embedded image (In the above formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹
Each independently hydrogen atom ^9, 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, R ^{1 3} or with the carbon atom to which 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, and R ^{1 5} 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]. 3. The cyclic olefin-based polymer (a) comprises:
It is selected from the group consisting of the following [A-1], [A-2] and [A-3], has a softening point (TMA) of 80 ° C. or higher, and has an intrinsic viscosity [η] of 0.05 to 10 dl /. g of the thermoplastic resin composition according to claim 2, wherein [A-1] is an α-olefin having 2 to 20 carbon atoms and represented by the formula (I) or (II). Α-olefin / cyclic olefin random copolymer obtained by copolymerizing with cyclic olefin, [A-2] ring-opened polymer or copolymer of cyclic olefin represented by formula (I) or (II) above And [A-3] a hydride of the above-mentioned [A-2] ring-opening polymer or copolymer. 4. [A] at least one thermoplastic resin selected from the following resins (a) to (c): (a) the following [A-1], [A-2] and [A-3] And a cyclic olefin polymer selected from the group consisting of [A-4], (b) a polycyclohexane resin, and (c) a 4-methyl-1-pentene polymer; [B] a polymer having a molecular weight of 2000 or less. A polyhydric alcohol having 6 or more carbon atoms in which the ratio of the number of carbon atoms to the number of hydroxyl groups in the same molecule is 1.5 to 30 (the polyhydric alcohol is
The molecule may contain an ether bond, a thioether bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Wherein the polyhydric alcohol [B] is contained in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin [A]. [A-1] α-olefin / cycloolefin random copolymer obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms with a cyclic olefin represented by the following formula (I) or (II): Polymer, embedded image (In the above formula (I), n is 0 or 1, m is 0 or an integer of 1 or more, q is 0 or 1, and R ¹ to
R ^18, R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, R ^{1 5} to R ¹⁸
In may form a monocyclic or polycyclic bonded to each other, and may be monocyclic or polycyclic have a double bond, also an R ^{1 5} and R ^{1 6} or R, ^{1 7} and with a R ^{1 8} may form an alkylidene group. ), Embedded image (In the above formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹
Each independently hydrogen atom ^9, 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, R ^{1 3} or with the carbon atom to which 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, and R ^{1 5} 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]. 5. The method according to claim 1, wherein the thermoplastic resin [A] comprises the following [A-
1], a ring selected from the group consisting of [A-2] and [A-3], having a softening point (TMA) of 80 ° C. or more and an intrinsic viscosity [η] of 0.05 to 10 dl / g. The thermoplastic resin composition according to claim 4, which is an olefin-based polymer; [A-1] an α-olefin having 2 to 20 carbon atoms and the formula (I) or (II). Α-olefin / cyclic olefin random copolymer obtained by copolymerizing with a cyclic olefin represented by the formula [A-2]: a ring-opened polymer of the cyclic olefin represented by the formula (I) or (II) or A copolymer, and [A-3] a hydride of the above [A-2] ring-opening polymer or copolymer. 6. The thermoplastic resin composition according to claim 1, wherein at least one hydroxyl group of the polyhydric alcohol is bonded to a primary carbon atom. 7. The thermoplastic resin composition according to claim 1, wherein the polyhydric alcohol is an aliphatic polyhydric alcohol. 8. A haze according to ASTM D1003 measured on a molded article having a thickness of 3 mm, which is formed from the thermoplastic resin composition according to claim 1, is 10%.
% Of the thermoplastic resin composition. 9. A thermoplastic resin molded article formed from the thermoplastic resin composition according to claim 1. Description: 10. A plastic lens comprising the thermoplastic resin composition according to claim 1. 11. A container comprising the thermoplastic resin composition according to claim 1. 12. A transparent sheet or a transparent board comprising the thermoplastic resin composition according to claim 1. 13. An optical recording medium comprising the thermoplastic resin composition according to claim 1.