JP2010163548A - Composite sheet and method for producing composite sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite sheet having a small linear expansion coefficient and thickness variation and containing a cycloolefin resin and a glass filler and a method for producing the composite sheet having the characteristics in high productivity. <P>SOLUTION: There is provided the composite sheet having a linear expansion coefficient of ≤30 ppm/K and a thickness difference between the maximum value and the minimum value of ≤10% of the average thickness and containing the cycloolefin resin and the glass filler. The composite sheet can be produced by extruding a mixture of the cycloolefin resin and the glass filler with an extruder in the form of a sheet under a condition satisfying the extrusion shear rate of 400-800 (1/min), wherein the extrusion shear rate is defined by formula (S): [extrusion shear rate (1/min)]=[take-off speed of sheet (m/min)]/[lip gap of the extrusion die (m)]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composite sheet containing a cyclic olefin-based resin and a glass filler, and a method for producing the composite sheet. More specifically, the present invention relates to a composite sheet containing a cyclic olefin-based resin and a glass filler, which is a heat-resistant transparent sheet suitable as a thin display, an optical functional sheet for electronic devices, a building material sheet, a substrate for electrical parts, and the like. And a method of manufacturing a composite sheet.

  Cyclic olefin resin is excellent in transparency, heat resistance, chemical resistance and the like. For this reason, the sheet made of the resin has attracted attention as an alternative substrate for an optical material and a glass substrate typified by an optical functional sheet for electronic devices such as thin displays and mobile phones.

  In order to apply a sheet made of such a cyclic olefin resin to a wider range of applications, shape stability during heating is required to cope with higher temperature manufacturing processes, and in particular, linear expansion of the sheet during heating. It is required to reduce the rate (linear expansion coefficient).

  For example, as a technique for producing a transparent sheet having a low coefficient of linear expansion by mixing a transparent resin and a glass filler, an epoxy or acrylic curable monomer is impregnated into a glass cloth, and the monomer is further heated. There is known a method for curing a sheet to form a sheet (see Patent Documents 1 and 2).

However, the above method requires a long heating step to cure the curable monomer, and has a problem that the productivity of the sheet is inferior.
In addition, by sandwiching a glass cloth coated with a cyclic olefin resin with a sheet made of a cyclic olefin resin and heating and pressing, a composite sheet of a cyclic olefin resin and a glass cloth having a low linear expansion coefficient can be obtained. It is known (see Patent Documents 3 and 4).

  However, the above method has a long manufacturing process, so that the productivity of the sheet is poor. In addition, the thickness unevenness of the sheet obtained due to pressure non-uniformity in the hot press process is large, and the optical properties of the sheet often vary. For this reason, there exists a problem that the said composite sheet is difficult to utilize as an optical material.

Japanese Patent No. 3728441 JP 2004-252435 A Japanese Patent No. 3265709 JP 2007-224270 A

  An object of the present invention is to provide a composite sheet containing a cyclic olefin-based resin and a glass filler having a small coefficient of linear expansion and thickness unevenness, and a method for producing a composite sheet having the above characteristics with high productivity.

The present inventors diligently studied to solve the above problems. As a result, it has been found that by forming a mixture of a cyclic olefin-based resin and a glass filler into a sheet by an extruder under specific conditions, a composite sheet having the above characteristics and excellent in productivity can be provided. The invention has been completed. That is, the present invention relates to the following [1] to [8].

  [1] A composite sheet containing a cyclic olefin-based resin and a glass filler, having a linear expansion coefficient of 30 ppm / K or less, and the difference between the maximum value and the minimum value of the sheet is 10% of the average thickness Composite sheet that is within.

[2] The composite sheet according to [1], wherein the glass filler is glass fiber.
[3] The composite sheet according to [1] or [2], wherein the cyclic olefin-based resin has a structural unit derived from a monomer represented by the following general formula (1).

［式（１）において、Ｒ¹〜Ｒ⁴は、それぞれ独立に水素原子、ハロゲン原子、炭素数１〜３０の１価の炭化水素基またはその他の１価の有機基を表す。Ｒ¹およびＲ²、またはＲ³
およびＲ⁴は、一体化して２価の有機基を形成してもよく、Ｒ¹〜Ｒ⁴のうち任意の２つは
、互いに結合して単環または多環を形成してもよい。ｍおよびｎは、それぞれ独立に０または正の整数を表す。］

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or other monovalent organic group having 1 to 30 carbon atoms. R ¹ and R ² or R ³
And R ⁴ may be combined to form a divalent organic group, and any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocycle or polycycle. m and n each independently represents 0 or a positive integer. ]

  [4] A mixture of the cyclic olefin-based resin and the glass filler is formed into a sheet shape by an extruder under a condition where the discharge shear rate represented by the following formula (S) is 400 to 800 (1 / min), A method for producing a composite sheet, wherein a difference between a maximum value and a minimum value is within 10% of an average thickness and a linear expansion coefficient is 30 ppm / K or less.

［５］前記ガラスフィラーが、ガラス繊維である前記［４］に記載の複合シートの製造方法。

[5] The method for producing a composite sheet according to [4], wherein the glass filler is glass fiber.

  [6] The method for producing a composite sheet according to [4] or [5], wherein the cyclic olefin-based resin has a structural unit derived from a monomer represented by the following general formula (1).

［式（１）において、Ｒ¹〜Ｒ⁴は、それぞれ独立に水素原子、ハロゲン原子、炭素数１〜３０の１価の炭化水素基またはその他の１価の有機基を表す。Ｒ¹およびＲ²、またはＲ³
およびＲ⁴は、一体化して２価の有機基を形成してもよく、Ｒ¹〜Ｒ⁴のうち任意の２つは
、互いに結合して単環または多環を形成してもよい。ｍおよびｎは、それぞれ独立に０または正の整数を表す。］

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or other monovalent organic group having 1 to 30 carbon atoms. R ¹ and R ² or R ³
And R ⁴ may be combined to form a divalent organic group, and any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocycle or polycycle. m and n each independently represents 0 or a positive integer. ]

  [7] The [6], wherein the cyclic olefin-based resin is a (co) polymer obtained by ring-opening (co) polymerizing the monomer represented by the general formula (1) and then hydrogenating the monomer. ] The manufacturing method of the composite sheet of description.

  [8] The method for producing a composite sheet according to any one of [4] to [7], wherein the cycloolefin resin and the glass filler are combined with an extruder to obtain a strand, and the strand And a step of forming a pellet into a sheet shape by an extruder under the condition that the discharge shear rate represented by the formula (S) is 400 to 800 (1 / min) Sheet manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the composite sheet containing the cyclic olefin resin and glass filler with a small linear expansion coefficient and thickness nonuniformity, and the said characteristic with sufficient productivity is provided. Such a composite sheet is excellent in transparency and shape stability during heating.

  That is, in the production method of the present invention, a composite sheet of a cyclic olefin resin and a glass filler is produced by extrusion molding under specific conditions. Since the method can be operated continuously without particularly requiring a heating step, it has excellent productivity and easy sheet thickness control.

  Therefore, according to the above method, a composite sheet containing a cyclic olefin resin and a glass filler, which has not been obtained in the past and has a small linear expansion coefficient and thickness unevenness, can be provided.

FIG. 1 is an explanatory diagram of a composite sheet manufacturing apparatus used in Example 1. FIG.

Hereinafter, the composite sheet and the method for producing the composite sheet of the present invention will be described in detail.
[Composite sheet]
The composite sheet of the present invention contains a cyclic olefin-based resin and a glass filler, has a linear expansion coefficient of 30 ppm / K or less, and the difference between the maximum value and the minimum value of the thickness is within 10% of the average thickness. It is characterized by being.

  The linear expansion coefficient of the composite sheet is 30 ppm / K or less, more preferably 25 ppm / K or less, and still more preferably 20 ppm / K or less. A composite sheet having a linear expansion coefficient in the above range can be suitably used as an alternative substrate for an optical material or a glass substrate. In the present invention, the linear expansion coefficient of the composite sheet is preferably as small as possible, but the lower limit is usually about 5 ppm / K.

  The average thickness of the composite sheet is preferably 10 to 800 μm, more preferably 20 to 500 μm, and still more preferably 40 to 300 μm. When the average thickness of the composite sheet is less than the above range, problems such as insufficient mechanical strength may occur when post-processing such as stretching is performed on the composite sheet. On the other hand, if the average thickness of the composite sheet exceeds the above range, it may be difficult to produce a sheet having uniform thickness, surface properties, and the like, and it may be difficult to wind up the obtained sheet.

  The thickness distribution (thickness unevenness) of the composite sheet is such that the difference between the maximum value and the minimum value of the thickness of the sheet is within 10% of the average thickness, preferably within 7%, more preferably within 5%; The difference between the maximum value and the minimum value of the thickness of the composite sheet is preferably within 20 μm, more preferably within 10 μm, and even more preferably within 6 μm. When the thickness distribution of the composite sheet exceeds the above value, variations in optical characteristics due to thickness non-uniformity may occur when used as an optical material such as an optical functional sheet. In the present invention, the thickness distribution (thickness unevenness) of the composite sheet is preferably as small as possible, but the lower limit is usually about 1% (in other words, about 1 to 2 μm).

  The total light transmittance of the composite sheet is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. A composite sheet having a total light transmittance in the above range can be suitably used as an optical material. In the present invention, the total light transmittance of the composite sheet is preferably as large as possible, but the upper limit is usually about 97%.

  The mechanical heat distortion temperature of the composite sheet is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 140 ° C. or higher. The upper limit is usually about 250 ° C. A composite sheet having a mechanical thermal deformation temperature in the above range can be suitably used as an optical material.

  In addition, the said physical property of a composite sheet is measured on the conditions described in the Example mentioned later. Moreover, the composite sheet having the above various physical properties can be easily produced by the method described in the section of [Production method of composite sheet] described later.

  As described above, the composite sheet of the present invention is excellent in transparency and shape stability during heating, and has a small linear expansion coefficient and uneven thickness. Therefore, the composite sheet is represented by an optical functional sheet for electronic devices such as thin displays and mobile phones. It is suitably used for optical materials, alternative substrates for glass substrates, building material sheets, electrical component substrates, and the like.

  Hereinafter, the cyclic olefin resin and glass filler used in the present invention will be described. In addition, the composite sheet of the present invention may contain an additive together with the above components.

<Cyclic olefin resin>
The cyclic olefin resin used in the present invention is obtained by ring-opening (co) polymerization or addition (co) polymerization of one or more cyclic olefin monomers and other monomers. Examples thereof include (co) polymers having a structural unit derived from a monomer represented by the following general formula (1) (hereinafter also referred to as “specific monomer (1)”) (for example, , The following (i)
~ (Vii)). Among these, the hydrogenated (co) polymer (iii) is preferable from the viewpoint of the heat resistance, weather resistance, moisture resistance, mechanical strength, and moldability of the resin.
(I) A ring-opening (co) polymer of the specific monomer (1).
(Ii) A ring-opening copolymer of the specific monomer (1) and a copolymerizable monomer.
(Iii) A hydrogenated (co) polymer of the ring-opening (co) polymer of (i) or (ii) above.
(Iv) A hydrogenated (co) polymer of a (co) polymer obtained by cyclization of the ring-opened (co) polymer of (i) or (ii) by Friedel-Craft reaction.
(V) A saturated copolymer of the specific monomer (1) and an unsaturated double bond-containing compound.
(Vi) an addition type (co) polymer of at least one monomer selected from the specific monomer (1), vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer, and hydrogen thereof Addition (co) polymer.
(Vii) An alternating copolymer of the specific monomer (1) and acrylate.

式（１）において、Ｒ¹〜Ｒ⁴は、それぞれ独立に水素原子、ハロゲン原子、炭素数１〜３０の１価の炭化水素基またはその他の１価の有機基を表す。Ｒ¹およびＲ²、またはＲ³お
よびＲ⁴は、一体化して２価の有機基を形成してもよく、Ｒ¹〜Ｒ⁴のうち任意の２つは、
互いに結合して単環または多環を形成してもよい。ｍおよびｎは、それぞれ独立に０または正の整数を表す。

In Formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group. R ¹ and R ² , or R ³ and R ⁴ may be combined to form a divalent organic group, and any two of R ^{1 to} R ⁴ are
They may be bonded to each other to form a monocycle or polycycle. m and n each independently represents 0 or a positive integer.

In the present invention, “integrate to form a divalent organic group” means that R ¹ and R ² form, for example, an alkylidene group (see the following formula (1 ′)).

上記炭化水素基が有する少なくとも１つの水素原子はハロゲン原子に置換されていてもよく；また、上記その他の１価の有機基としては、例えば、炭化水素基以外の極性を有する１価の極性基が挙げられる。

The hydrocarbon group may have at least one hydrogen atom substituted with a halogen atom; and the other monovalent organic group may be, for example, a monovalent polar group having a polarity other than a hydrocarbon group. Is mentioned.

  Examples of the monovalent polar group include a carboxyl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, a cyano group, and at least one hydrogen atom of these groups is a halogen atom. And a substituted group. These polar groups may be bonded via a linking group having no polarity such as a methylene group, and are divalent having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group. It may be bonded via a linking group.

  Among these polar groups, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, a halogenated alkoxycarbonyl group, and an allyloxycarbonyl group are preferable, and an alkoxycarbonyl group, a halogenated alkoxycarbonyl group, and an allyloxycarbonyl group are more preferable.

In the specific monomer (1), preferable R ^{1 to} R ⁴ , m, and n are described below.
R ¹ and R ³ are preferably each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, still more preferably Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 2 carbon atoms; R ² and R ⁴ are each independently preferably a hydrogen atom or other monovalent organic group, more preferably R ² and R ^At least one of ⁴ is a monovalent polar group.

In R ¹ and R ³ , the hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

Particularly, at least one of R ² and R ⁴ is a polar group (hereinafter referred to as “polar”), which is a polar group to which an alkoxycarbonyl group is bonded via an alkoxycarbonyl group or a linking group. Group (i) "). By using the specific monomer (1) having a polar group (i), a cyclic olefin resin having a high glass transition temperature (Tg) and a low hygroscopic property and excellent adhesion to various materials is obtained. can get.
_{- (CH 2) p COOR ···} (i)
In the formula (i), R represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms. The hydrocarbon group is preferably an alkyl group. Moreover, p is preferably 0 to 5, more preferably 0. A smaller value of p is preferable in that a cyclic olefin-based resin having a high glass transition temperature can be obtained, and a specific monomer (1) in which p is 0 is preferable in that the synthesis is easy.

Further, when R ² or R ⁴ is a polar group (i), a group bonded to the carbon atom to which the polar group (i) is bonded (for example, when R ² is a polar group (i)) R ¹ ) is preferably an alkyl group in that a cyclic olefin resin having low hygroscopicity can be obtained.

  m and n are each independently preferably an integer of 0 to 3, more preferably m + n = 0 to 4, more preferably an integer satisfying m + n = 0 to 2, particularly preferably m = 0, n. = 1. By using the specific monomer (1) in which m = 0 and n = 1, a cyclic olefin resin having a high glass transition temperature and excellent mechanical strength can be obtained.

  Specific examples of the specific monomer (1) include the following monomers, but the specific monomer (1) is not limited to these specific examples. Moreover, the specific monomer (1) may be used alone or in combination of two or more.

Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,

5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-isopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.

  In the present invention, the cyclic olefin-based resin can be obtained by a known method. For example, JP-A-1-132626, JP-A-1-240517, JP-A-2006-77257, and JP-A-2008-955. It can be obtained by the method described in the publication. Hereinafter, the ring-opening (co) polymers (I) and (II) and the hydrogenated (co) polymer (III) will be described.

-Ring-opening (co) polymers (I) and (II)-
The ring-opening (co) polymer (I) is synthesized by ring-opening (co) polymerizing one or more specific monomers (1). The ring-opening copolymer (II) is synthesized by ring-opening copolymerization of one or more specific monomers (1) and a copolymerizable monomer described below. At this time, it is preferable to use a ring-opening polymerization catalyst, a polymerization reaction solvent and a molecular weight regulator described below.

≪Copolymerizable monomer≫
Examples of the copolymerizable monomer (excluding a molecular weight regulator described later) include cycloolefins having 4 to 20 carbon atoms, preferably 5 to 12 carbon atoms. Specifically, cyclobutene, cyclopentene, cycloheptene, And cyclooctene. These copolymerizable monomers may be used alone or in combination of two or more.

  The amount of the copolymerizable monomer used is such that the specific monomer (1): copolymerizable monomer (weight ratio) is preferably 100: 0 to 50:50, more preferably 100: 0 to 60. : The amount is 40.

Also, conjugated diene compounds such as polybutadiene and polyisoprene; unsaturated hydrocarbons having two or more carbon-carbon double bonds in the main chain such as styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene, etc. The ring-opening copolymers (I) and (II) may be synthesized by ring-opening copolymerization of the specific monomer (1) or copolymerizable monomer in the presence of a system polymer or the like.

≪Ring-opening polymerization catalyst≫
As the ring-opening polymerization catalyst, a catalyst described in Olefin Metathesis and Metathesis Polymerization (KJ IVIN, JC MOL, Academic Press 1997) is preferably used.

  Examples of such a ring-opening polymerization catalyst include (a) at least one compound selected from compounds of W, Mo, Re, V and Ti (hereinafter, also referred to as “compound (a)”), b) A compound such as Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, Al, Si, Sn, Pb, etc., which has a bond between the element and carbon or a bond between the element and hydrogen. Examples thereof include a metathesis polymerization catalyst comprising a combination with at least one compound selected from at least one compound (hereinafter also referred to as “compound (b)”). Further, the ring-opening polymerization catalyst may contain an additive (c) described later in order to increase the activity of the catalyst.

Examples of the compound (a) include compounds described in JP-A-1-240517 (page 7) such as WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ and TiCl ₄ .
Examples of the compound (b) include n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, and (C ₂ H ₅ ) ₂ Al.
Cl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH
And the compounds described in JP-A-1-240517 (page 7).

  As the additive (c), for example, alcohols, aldehydes, ketones and amines can be suitably used, and further described in JP-A-1-240517 (page 7, lower right to page 8, upper left column). These compounds can be used.

  Further, in place of the metathesis polymerization catalyst composed of the above-mentioned compound (a), compound (b), additive (c) and the like, (d) a periodic table group 4-8 transition metal-carbene complex without using a promoter, A metathesis polymerization catalyst composed of a metallacyclobutane complex or the like (hereinafter also referred to as “other catalyst (d)”) may be used.

Examples of other catalysts (d) include W (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CH
tBu) (O tBu) ₂ , Mo (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CH tBu) (O tBu) ₂ , Ru (= CHCH = CPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (= CHPh) (PC ₆ H ₁₁ ) ₂ Cl ₂ .

  The amount of the ring-opening polymerization catalyst used is preferably compound (a): all monomers (referring to all monomers used when synthesizing a cyclic olefin resin; the same shall apply hereinafter) (molar ratio). The range is 1: 500 to 1: 500000, more preferably 1: 1000 to 1: 100000, and the compound (a): compound (b) (molar ratio in terms of metal atom) is preferably 1: 1 to 1. : 100, more preferably 1: 2 to 1:50. When the additive (c) is added to the ring-opening polymerization catalyst, the additive (c): the compound (a) (molar ratio) Is preferably in the range of 0.005: 1 to 15: 1, more preferably 0.05: 1 to 7: 1.

  The amount of the other catalyst (d) used is such that the other catalyst (d): total monomer (molar ratio) is preferably 1:50 to 1: 100000, more preferably 1: 100 to 1: 50000. This is the range.

≪Solvent for polymerization reaction≫
Examples of the solvent for the polymerization reaction include alkanes such as pentane, hexane, heptane, octane, nonane and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; benzene, toluene, xylene and ethylbenzene. , Aromatic hydrocarbons such as cumene; halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, aryl halides, etc .; ethyl acetate, n-butyl acetate, Saturated carboxylic acid esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane . Of these, aromatic hydrocarbons are preferred. Moreover, these solvent for polymerization reaction may be used individually by 1 type, and may use 2 or more types together.
The amount of the solvent for the polymerization reaction is such that the solvent: specific monomer (1) (weight ratio) is preferably 1: 1 to 10: 1, more preferably 1: 1 to 5: 1. The

≪Molecular weight regulator≫
The molecular weights of the ring-opening (co) polymers (I) and (II) can be adjusted by appropriately selecting the polymerization temperature, the type of the ring-opening polymerization catalyst, and the type of the solvent for the polymerization reaction. It is preferable to adjust by coexisting in the reaction system.

Examples of the molecular weight regulator include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene. . Of these, 1-butene and 1-hexene are particularly preferable. Moreover, these molecular weight regulators may be used individually by 1 type, and may use 2 or more types together.
The amount of the molecular weight regulator used is preferably 0.005 to 0.6 mol, more preferably 0.02 to 0.00 mol, per 1 mol of the specific monomer (1) subjected to the ring-opening polymerization reaction. 5 moles.

-Hydrogenated (co) polymer (III)-
The ring-opening (co) polymer (I) or ring-opening copolymer (II) obtained as described above can be used as it is, but a hydrogenated (co) polymer ( III) is useful because it is a resin with high impact resistance. In the hydrogenation, it is preferable to use a hydrogenation catalyst.

≪Hydrogenation catalyst≫
As said hydrogenation catalyst, the hydrogenation catalyst used for the hydrogenation reaction of a normal olefinic compound can be used. As the hydrogenation catalyst, any known heterogeneous catalyst and homogeneous catalyst can be used.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania.

  Examples of the homogeneous catalyst include nickel naphthenate / triethylaluminum, bis (acetylacetonato) nickel (II) / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, Chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, (acetoxy) carbonyl (hydrido) bis (triphenylphosphine) ) Ruthenium, (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium.

The shape of the hydrogenation catalyst may be powder or granular. Moreover, a hydrogenation catalyst may be used individually by 1 type, and may use 2 or more types together.
The amount of the hydrogenation catalyst used should be adjusted appropriately, but the total of the ring-opening (co) polymer (I) and the ring-opening copolymer (II): the hydrogenation catalyst (weight ratio) is preferred. Is an amount of 1: 1 × 10 ⁻⁶ to 1: 2.

-Physical properties of cyclic olefin resin-
The cyclic olefin-based resin used in the present invention has a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC), preferably 8000 to 100,000, more preferably 10,000 to 80000, and still more preferably 12000. 50000, the weight average molecular weight (Mw) is preferably 20000 to 300000, more preferably 30000 to 250,000, still more preferably 40000 to 200000, and the molecular weight distribution (Mw / Mn) is preferably 2.0 to 4.0. More preferably, it is 2.5-3.7, More preferably, it is 2.8-3.5. By using a cyclic olefin resin having a number average molecular weight and a weight average molecular weight within the above ranges, a composite sheet having excellent mechanical strength can be obtained. Moreover, the composite sheet excellent in mechanical strength can be obtained by using a cyclic olefin resin having a molecular weight distribution in the above range.

  The cyclic olefin resin used in the present invention has a glass transition temperature (Tg) of preferably 100 ° C. or higher, more preferably 100 to 350 ° C., still more preferably 110 to 250 ° C., and particularly preferably 110 to 200 ° C. If the Tg of the cyclic olefin-based resin is below the above range, the resin may be deformed when the resin is used under high temperature conditions or during secondary processing such as coating or printing. On the other hand, if the Tg of the cyclic olefin-based resin exceeds the above range, the molding process becomes difficult, and it becomes necessary to increase the heating temperature during the molding process, so that the resin may be deteriorated by heat.

<Glass filler>
Examples of the glass filler used in the present invention include glass fibers such as glass chopped strands; glass woven fabrics such as glass cloth; glass fiber fabrics such as glass nonwoven fabrics; glass beads; glass flakes; glass powder; . Among these, glass fibers are particularly preferable because they can be easily combined with the cyclic olefin-based resin by extrusion, and a composite sheet having excellent mechanical strength and heat resistance can be obtained.

  Although it does not specifically limit as said crow fiber, Although a well-known official thing can be used, it is preferable that the average length is 0.5-100 mm, and it is more preferable that it is 1-50 mm. When the average length of the glass fibers is within the above range, the glass fibers and the cyclic olefin-based resin can be easily combined in the extruder, and the linear expansion coefficient of the resulting composite sheet can be lowered.

  Moreover, the average fiber diameter of glass fiber becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 5-20 micrometers. If the average fiber diameter of the glass fiber is too small, the strength of the composite sheet obtained by breaking the glass fiber in the extruder is reduced, and if the average fiber diameter is too large, the surface property of the resulting composite sheet is reduced. There is.

  Examples of the glass include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, low dielectric constant glass, and high dielectric constant glass. Among these, E glass, S glass, and NE glass, which have few ionic impurities such as alkali metals and are easily available, are preferable.

  In order to improve the adhesion between the glass filler and the cyclic olefin resin, the glass filler surface is coated with a silane coupling agent such as aminosilane, styrylsilane, epoxysilane, methacryloxysilane, acryloxysilane, vinylsilane; You may process by metal chelate compounds, such as.

  When such a surface treatment is applied to the glass filler, the adhesiveness between the glass filler and the cyclic olefin-based resin is increased, so that the transparency of the composite sheet can be increased, and the composite sheet is repeated. It is possible to suppress a decrease in transparency due to interfacial peeling between the glass filler surface and a polymer such as a cyclic olefin resin that occurs when bending is applied.

  In this invention, content of a glass filler becomes like this. Preferably it is 66-132 weight part with respect to 100 weight part of cyclic olefin resin, More preferably, it is 80-120 weight part, More preferably, it is 90-110 weight part. The composite sheet in which the ratio of the content of the cyclic olefin resin and the glass filler is in the above range has good physical properties such as a linear expansion coefficient.

<Additives>
In the present invention, together with the cyclic olefin resin and the glass filler, a thermoplastic resin other than the cyclic olefin resin, an antioxidant, an ultraviolet absorber, a dye, a pigment, and a glass filler as long as the object of the present invention is not impaired. Other inorganic fillers may be used.

[Production method of composite sheet]
In the method for producing a composite sheet of the present invention, a mixture of a cyclic olefin-based resin and a glass filler is sheeted by an extruder under a discharge shear rate of 400 to 800 (1 / min) represented by the following formula (S). A composite sheet having a difference between a maximum value and a minimum value within 10% of the average thickness and having a linear expansion coefficient of 30 ppm / K or less is manufactured.

ここで、製造される複合シートの、厚み分布など（厚み平均、厚みの最大値と最小値との差）、線膨張係数、全光線透過率および機械的変形強度などの各種物性の好ましい範囲は、上記〔複合シート〕の欄に記載したとおりである。

Here, preferred range of various physical properties such as thickness distribution (thickness average, difference between maximum and minimum values of thickness), linear expansion coefficient, total light transmittance and mechanical deformation strength of the composite sheet to be manufactured is , As described in the above [Composite Sheet] column.

  As an extrusion molding method used in the present invention, for example, a cyclic olefin-based resin and a glass filler are compounded by an extruder, and the obtained complex is quantitatively supplied to a die by a gear pump and molded into a sheet, and cooled. A method of cooling a composite sheet obtained using a take-up machine such as a roll or a cooling belt (hereinafter also referred to as “cooling roll”) and winding the composite sheet using a winder is preferred.

  In the present invention, the order of supplying the cyclic olefin-based resin and the glass filler to the extruder is not particularly limited, and a resin composition containing the cyclic olefin-based resin and the glass filler may be supplied to the extruder. The olefin resin and the glass filler may be separately supplied to the extruder, or pellets containing the cyclic olefin resin and the glass filler may be supplied to the extruder.

In particular, it is preferable to supply pellets obtained by melting and mixing the cyclic olefin-based resin and the glass filler in advance using an extruder to the extruder again.
That is, the method for producing a composite sheet of the present invention includes (1) a step of obtaining a strand by compounding a cyclic olefin-based resin and a glass filler by an extruder, and (2) a step of obtaining a pellet by cutting the strand. (3) It is preferable to include a step of forming the pellets into a sheet shape by an extruder under the condition that the discharge shear rate represented by the formula (S) is 400 to 800 (1 / min).

  As described above, by melting and mixing the cyclic olefin resin and the glass filler twice in the extruder, the dispersibility of the glass filler contained in the composite sheet becomes high and uniform, and a composite sheet having high mechanical strength is obtained. .

  In the method for producing a composite sheet of the present invention, the cyclic olefin resin and the glass filler described in the above [Composite sheet] can be preferably used as the cyclic olefin resin and the glass filler. Moreover, you may use the said additive with the said cyclic olefin resin and a glass filler.

  In this invention, the supply ratio of a glass filler becomes like this. Preferably it is 66-132 weight part with respect to 100 weight part of cyclic olefin resin, More preferably, it is 80-120 weight part, More preferably, it is 90-110 weight part. When the supply ratio of the cyclic olefin-based resin and the glass filler is in the above range, physical properties such as a linear expansion coefficient of the obtained composite sheet are improved.

≪Extruder≫
Examples of the extruder include single-screw, twin-screw, planetary, conical, and Banbury mixer types. Among these, single-screw extruders and twin-screw extruders are preferably used. Examples of the screw shape of the extruder include a vent type, a tip dull mage type, a double flight type, a full flight type, and a barrier type; examples of the compression type include a slow compression type and a rapid compression type. Among these, the full flight type slow compression type or the barrier type slow compression type is preferable.

  The material of the extruder (cylinder, screw, etc.) and die is not particularly limited, and examples thereof include steel such as SCM and stainless steel such as SUS. In addition, as the above-mentioned extruder and die, the surface (extruder cylinder and inner surface of the die, the surface of the extruder screw) is plated with chromium, nickel, titanium, etc .; PVD (Physical Vapor Deposition) method Films such as TiN, TiAlN, TiCN, CrN, DLC (diamond-like carbon) formed by thermal spraying; tungsten-based materials such as WC and ceramics such as cermets are sprayed; nitriding treatment It can also be used. By performing such a surface treatment, the friction coefficient between the inner surface and the surface and the resin is reduced, so that a uniformly molten resin can be obtained.

  The resin temperature (referring to the set temperature of the extruder cylinder) is preferably 200 to 350 ° C, more preferably 220 to 320 ° C. If the resin temperature is below the above range, the resin cannot be uniformly melted. On the other hand, if the resin temperature is above the above range, it is difficult to produce a high-quality composite sheet having excellent surface properties due to thermal degradation of the resin during melting. May be.

  Further, the resin temperature is particularly preferably within the above temperature range and within the range of Tg + 120 ° C. to Tg + 160 ° C. with respect to the glass transition temperature (Tg) of the cyclic olefin resin. For example, when the Tg of the cyclic olefin-based resin is 130 ° C., a particularly preferable temperature range for the production of the composite sheet is 250 to 290 ° C. In the present invention, preferably, when the above-mentioned specific cyclic olefin resin is used, crystallization (white turbidity) of the composite sheet can be suppressed even at a high temperature as described above, and the resin is a glass filler. Therefore, the extrusion moldability is good.

  Moreover, the shear rate which a screw gives to resin at the time of extrusion becomes like this. Preferably it is 1-500 (1 / sec), More preferably, it is 2-350 (1 / sec), More preferably, it is 5-200 (1 / sec). If the shear rate at the time of extrusion is less than the above range, the resin cannot be uniformly melted, so that it may be difficult to obtain a composite sheet with small thickness unevenness. On the other hand, if the shear rate at the time of extrusion exceeds the above range, the shear force is too large, the resin and additives are decomposed and deteriorated, and defects such as foaming, die lines and deposits may occur on the surface of the composite sheet. is there.

≪Gear pump≫
As the gear pump, there are an internal lubrication system in which the resin returned from the downstream side between the gears enters the chia pump system and an external lubrication system in which the resin is discharged to the outside, but the thermal stability of the cyclic olefin resin Is not good, the external lubrication method is preferred. As for the gear teeth of the gear pump, the helical type is preferable to the type parallel to the shaft because the measurement of the resin is stable.

≪Die≫
The shape of the die is preferably a shape that can make the resin flow inside the die uniform. Further, in order to make the thickness of the composite sheet uniform, the pressure distribution inside the die in the width direction near the die outlet is constant, and the resin flow rate in the width direction near the die outlet is almost constant, It is preferable that the resin flow rate at the outlet is in a range that can be adjusted by the lip gap of the discharge port (the opening amount of the die lip; hereinafter, also simply referred to as “lip gap”).

As a die manifold that satisfies the above conditions, a coat hanger type manifold is preferable. On the other hand, in the manifolds such as the straight type and the fishtail type, the flow rate distribution of the resin flow rate in the width direction is increased, and as a result, the thickness unevenness of the composite sheet may be increased.

  In the present invention, the discharge shear rate (1 / min) represented by the ratio between the sheet take-up speed (m / min) and the lip gap (m) in the die lip during extrusion is set in the following specific range. Then, the mixture or composite of the cyclic olefin resin and the glass filler is formed into a sheet shape by an extruder.

  In the prior art, the general cyclic olefin-based resin extrusion conditions were such that the discharge shear rate was about 10,000 to 20000 (1 / min). However, if the above conditions are applied to a composite of a cyclic olefin resin and a glass filler, the take-up speed is too high to form a sheet at all.

  Further, in order to produce a composite sheet having a low coefficient of linear expansion, it is necessary in the prior art to supply 30% by weight or more of glass filler with respect to the total amount of cyclic olefin resin and glass filler. It was. And at such a supply ratio, since the melting characteristics of these composites are poor (MFR reduction, toughness reduction), it has been considered difficult to form the composites into a sheet by extrusion molding.

  However, in the present invention, the above problems have been solved by extrusion molding under specific conditions (for example, sheet molding is possible even if the above amount of glass filler is supplied). That is, by extruding a mixture or composite of a cyclic olefin-based resin and a glass filler under the following conditions, excellent transparency and shape stability during heating, linear expansion A composite sheet with small coefficient and thickness unevenness can be manufactured.

上記式（Ｓ）で表される押出時の吐出せん断速度は、４００〜８００（１／ｍｉｎ）、好ましくは５００〜７００（１／ｍｉｎ）、特に好ましくは５５０〜６５０（１／ｍｉｎ）である。吐出せん断速度が前記範囲より小さいと、押出機のダイリップ付近で樹脂だまりが形成され、局所的に厚い部分が形成され、厚みの均一なシートを製造することが困難となる。一方、吐出せん断速度が前記範囲より大きいと、シート内に薄い部分や空隙が形成され、シートの巻取り問題などが発生し、シート状への成形が困難となる。

The discharge shear rate during extrusion represented by the above formula (S) is 400 to 800 (1 / min), preferably 500 to 700 (1 / min), and particularly preferably 550 to 650 (1 / min). . If the discharge shear rate is smaller than the above range, a resin pool is formed in the vicinity of the die lip of the extruder, a locally thick portion is formed, and it becomes difficult to produce a sheet having a uniform thickness. On the other hand, when the discharge shear rate is larger than the above range, a thin portion or a gap is formed in the sheet, and a sheet winding problem or the like occurs, making it difficult to form the sheet.

  In order to make the thickness of the composite sheet uniform, it is important to make the temperature distribution in the width direction in the vicinity of the die exit constant, and the temperature distribution is preferably ± 1 ° C. or less, more preferably ± 0.5. It is below ℃. If the temperature distribution in the width direction in the vicinity of the die exit is outside the above range (if temperature unevenness occurs), a difference occurs in the melt viscosity of the resin, resulting in thickness unevenness and stress distribution unevenness in the resulting composite sheet. Sometimes.

  Furthermore, the lip gap is preferably 0.3 to 1.5 mm, more preferably 0.3 to 1.2 mm, and still more preferably 0.35 to 1.0 mm. If the lip gap is less than the above range, the resin pressure inside the die becomes too high, and resin leakage may occur from places other than the die lip. On the other hand, if the lip gap exceeds the above range, the resin pressure inside the die is difficult to increase, and the thickness uniformity in the width direction of the composite sheet may deteriorate.

  Moreover, the preferable range of the set temperature of the discharge port is the same as the preferable range of the resin temperature, and is within the range of Tg + 120 ° C. to Tg + 160 ° C. with respect to the glass transition temperature (Tg) of the cyclic olefin resin. Is particularly preferred.

<< Molding of composite sheet >>
The molten resin is discharged from a die lip (discharge port), and is adhered and solidified to the cooling roll or the like to be molded into a target composite sheet. Examples of the method for improving the adhesion between the molten resin extruded from the die lip and the cooling roll include a nip roll method, an electrostatic application method, an air knife method, a vacuum chamber method, a calendar method, and the thickness of the composite sheet. An appropriate method is selected according to the application.

  Various surface treatments are preferably performed on the surface of the cooling roll or the like used to solidify the molten resin extruded from the die lip as well as the extruder cylinder and the inner surface of the die.

  The manufacturing method of the composite sheet of the present invention described above requires a shorter manufacturing process than the conventional manufacturing method having a hot press process and does not require the hot press process, and thus the thickness unevenness of the composite sheet obtained Is small. For this reason, the optical properties of the composite sheet are less likely to vary, and the composite sheet is suitably used as the optical material.

  Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these. In the examples, “parts” represents “parts by weight” unless otherwise specified.

Various physical properties were measured according to the methods described in (1) to (7) below.
(1) Hydrogenation rate (%)
An AVANCE 500 (manufactured by Bruker) was used as a nuclear magnetic resonance spectrometer (NMR), and ¹ H-NMR of a cyclic olefin resin was measured using d-chloroform as a measurement solvent. The hydrogenation rate (%) of the resin is based on the integral value of 5.1 to 5.8 ppm of vinylene group, 3.7 ppm of methoxy group, and 0.6 to 2.8 ppm of aliphatic proton. Is a value obtained by calculating.

(2) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the cyclic olefin resin was measured using DSC6200 (manufactured by Seiko Instruments Inc.) at a heating rate = 20 ° C./min under nitrogen flow, and the maximum peak temperature (A Point) and a temperature of −20 ° C. from the maximum peak temperature (point A) (point B) are plotted on the differential scanning calorimetry curve, and the tangent line on the baseline starting from point B and the tangent line starting from point A Is the value obtained as the intersection of

(3) Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)
Gel permeation chromatography (HLC-8220GPC manufactured by Tosoh Corp., column: guard column H _XL- H manufactured by Tosoh Corp., TSKgel G7000H _XL , two TSKgel GMH _XL , TSKgel G2000H _XL , solvent: Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by weight, injection amount: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard material: manufactured by Tosoh Corporation The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) of the cyclic olefin resin were measured using TSK standard polystyrene.

(4) Thickness of composite sheet In the central part of the composite sheet, measurement points are set at 1 cm intervals on a straight line connecting two 10 cm intervals in the direction perpendicular to the molding direction, and the thickness of the sheet is measured with a micrometer ( Measured with Mitutoyo Corporation. The average thickness of the measured composite sheet is the average thickness of the composite sheet, the difference between the maximum value and the minimum value is the uneven thickness of the composite sheet (1), and the difference between the maximum value and the minimum value with respect to the average thickness is the uneven thickness of the composite sheet. (2).

(5) Mechanical heat distortion temperature Using a thermomechanical apparatus (TMA; Thermal Mechanical Analysis) / SS6100 (manufactured by Seiko Instruments Inc.), a composite sheet prepared to a width of 4 mm and a length of 20 mm is obtained from 25 ° C. to 350 ° C. A tensile test was performed in the long-side direction with an applied load of 10 g while raising the temperature at ° C./min. The elongation ratio of the composite sheet was recorded, and the temperature at which the elongation ratio began to increase rapidly due to the softening of the composite sheet was determined by the tangential method, and the temperature was defined as the mechanical thermal deformation temperature of the composite sheet.

(6) Linear expansion coefficient Using a thermomechanical device (TMA; Thermal Mechanical Analysis) / SS6100 (manufactured by Seiko Instruments Inc.), a composite sheet prepared to have a width of 10 mm and a length of 10 mm is 25 ° C. → 150 ° C. → 25 ° C. → While heating and cooling at a rate of 10 ° C./min with a temperature profile of 300 ° C., an applied load was set to 1 g, and a compression test was performed in parallel to the sheet surface. The linear expansion coefficient (ppm / K) of the sheet was obtained by dividing the elongation amount on the parallel surface of the composite sheet in the temperature range of 50 ° C. to 150 ° C. at the second temperature increase by 100.

(7) Total light transmittance The total light transmittance (%) of the composite sheet is a value measured using a haze-light transmittance measuring machine (Haze-Gard Plus type) manufactured by Gardner in accordance with ASTM 1003 standard. It is.

[Synthesis Example 1]
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (2) [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene (DNM) and 225 parts, and bicyclo [2.2.1] hept-2-ene (NB) 25 parts of the following formula (3), 1-hexene (molecular weight 27 parts of a regulator and 200 parts of toluene (polymerization reaction solvent) were charged into a nitrogen-substituted reaction vessel, and the solution was heated to 80 ° C.

  Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (0.025 mol / liter) were added to the solution in the reaction vessel as a ring-opening polymerization catalyst. 0.9 part) was added, and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

このようにして得られた開環重合体溶液１０００部をオートクレーブに仕込み、該開環重合体溶液に、水素添加触媒としてＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．１２部添加し、水素ガス圧１００ｋｇ／ｃｍ²、反応温度１６５℃の条件下で、３時間加熱撹拌
して水素添加反応を行った。

1000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ as a hydrogenation catalyst was added to the ring-opening polymer solution in an amount of 0.12 A hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin (A)”).

  The hydrogenation rate of the resin (A) thus obtained was 99.9%, the glass transition temperature was 130 ° C., the number average molecular weight (Mn) was 20800, the weight average molecular weight (Mw) was 62000, and the molecular weight distribution (Mw / Mn) was 3.0.

[Production Example 1]
A glass separable flask equipped with a stirring blade was charged with 100 parts of resin (A), 300 parts of toluene was added thereto, and stirred at room temperature for 5 hours to dissolve the resin (A) in toluene.

  To this resin solution, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate as an antioxidant was added in an amount of 0.000 to 100 parts of resin (A) in the resin solution. 5 parts were added, and the resin solution was filtered using a membrane filter (manufactured by ADVANTEC) having a pore size of 5 μm.

  The obtained resin solution was cast at 25 ° C. using an applicator so that the thickness after drying was 100 μm, allowed to stand at room temperature for 12 hours to evaporate the solvent, and then at 80 ° C. under vacuum for 2 hours. Furthermore, it hold | maintained at 150 degreeC for 12 hours, and obtained the resin film (A).

[Example 1]
<Manufacture of pellets>
Resin (A) 50 parts as cyclic olefin-based resin, NE glass chopped strand (manufactured by Nittobo) as glass filler, and pentaerythrityl tetrakis [3- (3,5-di-t- (Butyl-4-hydroxyphenyl)] propionate (0.5 part) is charged into a hopper of a twin screw extruder (TEM-37BS, manufactured by Toshiba Machine Co., Ltd.), the cylinder temperature is 290 ° C., the shaft rotation speed is 100 rpm, and the extrusion speed. The strand was extruded at 10 to 20 kg / hr, and the strand was cut with a strand cutter (PPS-150R type, manufactured by Toshiba Machine Co., Ltd.) to obtain a cyclic olefin resin-glass fiber composite pellet.

<Extrusion conditions for composite sheet>
The cyclic olefin resin-glass fiber composite pellets were extrusion molded under the conditions shown below (see FIG. 1) to obtain a cyclic olefin resin-glass fiber composite sheet. Table 1 shows the physical property values according to the above (4) to (7) of the obtained composite sheet.
Extruder: KZW15TW-30MG-NH type twin screw extruder (manufactured by Technobel Corp.).
・ Cylinder inner diameter: 15 (mm)
・ Cylinder set temperature: 285 (℃)
-Screw shape: Full flight type-Screw L / D: 30
・ Compression type: Slow compression type, compression ratio 2.5
Extrusion amount: 16 (kg / hr)
-Shear rate: 100 (1 / s)
Die: Coat hanger type manifold. Die inner surface with chrome plating.・ Width of discharge port: 300 (mm)
・ Lip gap of discharge port: 0.5 (mm)
・ Set temperature of discharge port: 270 (℃)
・ Discharge shear rate: 620 (1 / min)
Film winding device: FPU15-330 type film winding device (manufactured by Technobel).
-Roll surface length: 330 (mm)
Sheet take-off speed: 0.31 (m / min)
・ Touch roll: Material (S45C) + Surface treatment (HCr plating)
・ Cooling roll: Material (S45C) + Surface treatment (HCr plating)
・ Peeling roll: Material (S45C) + Surface treatment (HCr plating)
・ Nip roll: Material (silicon rubber)
・ Take-up roll: Material (S45C) + Surface treatment (HCr plating)

[Comparative Example 1]
In Example 1, extrusion molding was carried out in the same manner as in Example 1 except that the sheet take-up speed was 0.5 (m / min) and the discharge shear rate was 1000 (1 / min). However, voids and thinning were observed in the obtained sheet, and a good sheet could not be obtained.

[Comparative Example 2]
In Example 1, extrusion molding was carried out in the same manner as in Example 1 except that the sheet take-up speed was 0.1 (m / min) and the discharge shear rate was 200 (1 / min). However, the obtained sheet showed a large wave parallel to the take-up direction, and a good sheet was not obtained.

[Comparative Example 3]
Cyclic olefin resin-glass fiber composite pellets obtained in the same manner as in Example 1 were preheated at 300 ° C. × 10 min, pressurized 30 MPa × 300 ° C. × 5 min with a vacuum press (PEWR-1030 manufactured by Kansai Roll Co., Ltd.). To obtain a cyclic olefin-based resin-glass fiber composite sheet. Table 1 shows the physical property values according to the above (4) to (7) of the obtained composite sheet.

[Comparative Example 4]
With reference to Japanese Patent No. 3265709, sandwiched between a resin film (A) (thickness: 100 μm) and a NE glass cloth (manufactured by Nittobo Co., Ltd.) having a thickness of 100 μm coated with a 1% toluene solution of resin (A) in advance. After that, with a vacuum press machine (PEWR-1030 type manufactured by Kansai Roll Co., Ltd.), it was pressed with preheating 300 ° C. × 10 min and pressurization 30 MPa × 300 ° C. × 5 min to prepare a cyclic olefin resin-glass composite sheet. . Table 1 shows the physical property values according to the above (4) to (7) of the obtained composite sheet.

表１に示すように、吐出せん断速度が本発明で規定される範囲外で実施された比較例１や２は、良好な複合シートを得ることができなかった。これは、環状オレフィン系樹脂とガラスフィラーとの複合化物では、吐出せん断速度が特定の範囲にある条件において押出成形しなければ良好な複合シートを製造することができないことを意味し、本発明の有意性を示すものである。

As shown in Table 1, Comparative Examples 1 and 2 carried out with the discharge shear rate outside the range defined by the present invention could not obtain a good composite sheet. This means that a composite of a cyclic olefin resin and a glass filler cannot produce a good composite sheet unless it is extruded under conditions where the discharge shear rate is in a specific range. Shows significance.

  Moreover, the cyclic olefin resin-glass fiber composite sheet obtained by molding with an extruder has smaller thickness unevenness (4) and transparency (7), heating than the composite sheet obtained by press molding. The shape stability at the time (5) and the linear expansion coefficient (6) are equivalent.

10 ... Extruder 20 ... Die 21 ... Die lip (discharge port)
30 ... Molten resin 40 ... Cooling roll 50 ... Touch roll 60 ... Peeling roll 70 ... Take-up roll 80 ... Nip roll 90 ... Dancer roll 100 ... Winding machine 110 ... Winding device

Claims (8)

  A composite sheet containing a cyclic olefin-based resin and a glass filler, having a linear expansion coefficient of 30 ppm / K or less, and the difference between the maximum value and the minimum value of the sheet being within 10% of the average thickness Composite sheet.   The composite sheet according to claim 1, wherein the glass filler is glass fiber. The composite sheet according to claim 1 or 2, wherein the cyclic olefin-based resin has a structural unit derived from a monomer represented by the following general formula (1).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or other monovalent organic group having 1 to 30 carbon atoms. R ¹ and R ² or R ³
And R ⁴ may be combined to form a divalent organic group, and any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocycle or polycycle. m and n each independently represents 0 or a positive integer. ] The mixture of the cyclic olefin resin and the glass filler is formed into a sheet shape by an extruder under the condition that the discharge shear rate represented by the following formula (S) is 400 to 800 (1 / min), A composite sheet manufacturing method for manufacturing a composite sheet having a difference from a minimum value within 10% of an average thickness and having a linear expansion coefficient of 30 ppm / K or less.

  The method for producing a composite sheet according to claim 4, wherein the glass filler is glass fiber. The method for producing a composite sheet according to claim 4 or 5, wherein the cyclic olefin-based resin has a structural unit derived from a monomer represented by the following general formula (1).

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, or other monovalent organic group having 1 to 30 carbon atoms. R ¹ and R ² or R ³
And R ⁴ may be combined to form a divalent organic group, and any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocycle or polycycle. m and n each independently represents 0 or a positive integer. ]   The cyclic olefin resin is a (co) polymer obtained by ring-opening (co) polymerizing the monomer represented by the general formula (1) and then hydrogenating the monomer. A method for producing a composite sheet.   It is the manufacturing method of the composite sheet in any one of Claims 4-7, Comprising: The process which combines the said cyclic olefin resin and glass filler with an extruder, and obtains a strand, This strand is cut | judged and pellets are cut | disconnected. The manufacturing method of a composite sheet including the process of obtaining, and the process of shape | molding this pellet to a sheet form with an extruder on the conditions whose discharge shear rate represented by said Formula (S) is 400-800 (1 / min).

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