KR20070078384A - Transparent complex and process for producing the same - Google Patents

Abstract

A transparent complex is provided to be superior in colorless transparency and heat resistance, to have a low coefficient of linear expansion, and to be substitutable for glass having small optical anisotropy. The transparent complex contains (A) a cyclic olefin-based thermoplastic resin and (B) glass fiber cloth. The cyclic olefin-based thermoplastic resin comprises at least one selected from (A1) a ring-opened polymer of at least one monomer represented by the following chemical formula 1, (A2) a ring-opened polymer of at least one monomer copolymerizable with at least one monomer represented by the following chemical formula 1, and (A3) a (co)polymer obtained by hydrogenating the ring-opened polymer(A1) or the ring-opened copolymer(A2).

Description

Transparent composite and its manufacturing method {TRANSPARENT COMPLEX AND PROCESS FOR PRODUCING THE SAME}

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-77321

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-90667

[Patent Document 3] Japanese Patent Application Laid-Open No. 5-140376

The present invention relates to a transparent composite that is colorless, excellent in transparency and heat resistance, small in coefficient of linear expansion, and capable of replacing glass with low optical anisotropy.

Generally, glass plates are widely used for liquid crystal display elements such as an active matrix type, display element substrates for organic EL display elements, color filter substrates, solar cell substrates, and the like. However, various plastic materials have recently been considered as alternatives for glass plates because they are fragile, do not bend, and have a specific gravity that is not suitable for light weight.

For example, Patent Document 1 (Japanese Patent Laid-Open No. Hei 10-77321) discloses an active energy ray with respect to a resin composition containing an amorphous thermoplastic resin and bis (meth) acrylate capable of curing an active energy ray. It is described that the member which hardened using can be used for glass substrate substitutes, such as a liquid crystal substrate.

Moreover, the said patent document 2 (Unexamined-Japanese-Patent No. 10-90667) discloses the transparent substrate which hardened-molded the composition containing specific bis (meth) acrylates, such as an alicyclic structure and aromatics, by active energy ray etc. The used liquid crystal display element is described.

However, all of these glass-replacement plastic materials have considerably larger coefficients of linear expansion than glass plates, which, when used in display element substrates, particularly active matrix display element substrates, may cause deficiencies such as warpage and disconnection of aluminum wiring in the manufacturing process. The use of the furnace was difficult.

In addition, a display element substrate, particularly an active matrix display element substrate, is required to have a material having low transparency, heat resistance, and linear expansion coefficient. In the case of using a plastic material, in order to reduce the linear expansion coefficient, glass powder or glass fiber is conventionally used in resin. Compounding of the materials for mixing inorganic fillers such as these is also performed in various ways.

However, in the conventional mixing of the resin and the inorganic filler, transparency of the substrate was often impaired. This is mainly because the size of the inorganic filler is larger than visible light or the refractive indexes of the resin and the inorganic filler are different, so that light transmitted through the resin is refracted.

Accordingly, Patent Document 3 (Japanese Patent Laid-Open No. 5-140376) includes a polymer and a glass filler containing a specific maleimide structural unit and an alkylene structural unit, and the difference in refractive index between the resin and the glass filler is within 0.01. A transparent resin composition is disclosed.

However, in the resin composition described in Patent Document 3, the strength and toughness are insufficient, and it is difficult to form, for example, roll-to-roll molding of a thin film of 500 μm or less, especially 200 μm or less, and even molding is possible. Many problems have arisen from the standpoint of not being able to withstand repeated bending in various manufacturing processes and use steps thereafter.

Under such a situation, there has been a demand for the appearance of a transparent composite having excellent colorless transparency and heat resistance, small coefficient of linear expansion, and small glass anisotropy.

Therefore, as a result of earnestly examining in order to provide the transparent composite suitable for such optical use, the cyclic olefin thermoplastic resin has high heat resistance, colorlessness, high transparency, and small optical anisotropy. It has been found preferred as a plastic material.

Moreover, by compounding this cyclic olefin thermoplastic resin and glass fiber cloth, it has high transparency, colorlessness, excellent transparency, heat resistance and solvent resistance, small optical anisotropy, and low coefficient of linear expansion, for example, having a wavelength of 400 nm. It was found that a transparent composite having a light transmittance of 80% or more and excellent transparency and a small optical anisotropy having a linear expansion coefficient at 50 to 140 ° C. of 60 ppm / ° C. or less was obtained, thus completing the present invention.

That is, the structure of this invention is as follows.

(1) [A] cyclic olefin thermoplastic resin

[B] fiberglass cloth

Transparent composite, characterized in that it contains.

(2) the cyclic olefin thermoplastic resin,

[A1] Ring-opening polymer of one or more monomers (hereinafter also referred to as "specific monomers") represented by the following general formula (1);

[A2] Ring-opening copolymer with a monomer copolymerizable with a specific monomer; And

[A3] A (co) polymer formed by hydrogenating a ring-opening polymer [A1] or a ring-opening copolymer [A2]

Transparent composite containing at least one of.

In the formula, R ¹ To R ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 30 carbon atoms, or other monovalent organic groups, and may be the same or different, respectively, R ¹ and R ² Or R ³ and R ⁴ may be integrated to form a divalent hydrocarbon group, R ¹ or R ² and R ³ Alternatively, R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure, m is 0 or a positive integer, p is 0 or a positive integer, but p is 0 when m is 0.

(3) The transparent composite according to (1) or (2), wherein the glass fiber cloth is a glass cross.

(4) The surface treatment method of the glass fiber cloth characterized by drying, after immersing a glass fiber cloth in the solution (solid content concentration 3-50 weight%) in which the cyclic olefin thermoplastic resin melt | dissolved.

(5) glass fiber cloth is immersed in the solution (solid content concentration 3-50 weight%) in which the cyclic olefin thermoplastic resin melt | dissolved, and dried,

The obtained glass fiber cloth is sandwiched between two sheets containing the cyclic olefin thermoplastic resin and subjected to heat compression molding.

(6) Glass fiber cloth is immersed in the solution (solid content concentration 3-50 weight%) in which the cyclic olefin thermoplastic resin melt | dissolved, and the said resin solution is apply | coated and dried on one side or both surfaces of the obtained surface-treated glass fiber cloth. The manufacturing method of the transparent composite made into.

Best Mode for Carrying Out the Invention

The transparent composite according to the present invention includes a specific cyclic olefin thermoplastic resin and glass fiber cloth.

[Cyclic olefin thermoplastic resin]

The cyclic olefin thermoplastic resin used in the present invention is a ring-opening polymer of [A1] specific monomer, a ring-opening copolymer of [A2] specific monomer and a monomer copolymerizable with the monomer, and [A3] ring-opening (co) polymer thereof. It is preferable to contain 1 or more types chosen from the (co) polymer which hydrogenates.

<Specific monomer>

Although the following compounds are mentioned as a specific example of the said specific monomer, This invention is not limited to these specific examples.

Bicyclo [2.2.1] hept-2-ene,

Tricyclo [4.3.0.1 ^2,5 ] -3-decene,

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

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-ethylidenebicyclo [2.2.1] hept-2-ene,

5-phenylbicyclo [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,

8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-phenyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, etc. are mentioned.

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-heptafluoro-isopropyl-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,

(Ethoxycarbonyl 2,2,2-trifluoroethyl) 8-methyl-8 and the like can be mentioned tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene.

These can be used individually by 1 type or in combination of 2 or more types.

Among the specific monomers, R ¹ and R ^{3 in} Formula 1 are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms, and R ² and R ⁴ are A hydrogen atom or a monovalent organic group, at least one of R ² and R ⁴ represents a polar group other than a hydrogen atom or a hydrocarbon group, m is an integer of 0 to 3, p is an integer of 0 to 3, and more preferably m + p = 0-4, More preferably, it is 0-2, Especially preferably, m = 1, p = 0. The specific monomer whose m = 1 and p = 0 is preferable at the point that the glass transition temperature of the cyclic olefin thermoplastic resin obtained is high, and mechanical strength is also excellent.

As a polar group in the said specific monomer, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an amide group, a cyano group, etc. are mentioned, These polar groups can also couple | bond via a coupling group, such as a methylene group. Moreover, the hydrocarbon group etc. which the bivalent organic group which has polarity, such as a carbonyl group, an ether group, a silyl ether group, a thioether group, an imino group, are couple | bonded as a linking group, are also mentioned as a polar group. In these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is especially preferable.

In addition, R ² and R ⁴ One or more of the general formula are preferred in that they are (CH _{2) n} polar group of monomers represented by COOR is, has excellent adhesion to the obtained cyclic olefin-based thermoplastic resin is a high glass transition temperature and low moisture absorption, a variety of materials. In the above formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably an alkyl group. In addition, n is usually 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the cyclic olefin thermoplastic resin obtained is higher, and a particular monomer having n of 0 is preferable in that its synthesis is easy. .

In addition, in Chemical Formula 1, R ¹ Or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2, in particular a methyl group, and in particular, the alkyl group is represented by the above formula-(CH ₂ ) _n COOR Bonding to the same carbon atom as the carbon atom which the specific polar group couple | bonded is preferable at the point which can lower the hygroscopicity of the obtained cyclic olefin thermoplastic resin.

<Copolymerizable monomer>

Specific examples of the copolymerizable monomers include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and dicyclopentadiene. As carbon number of a cycloolefin, 4-20 are preferable and 5-12 are more preferable. These can be used individually by 1 type or in combination of 2 or more types.

The preferable use range of a specific monomer / copolymerizable monomer is 100/0-50/50 by weight ratio, More preferably, it is 100/0-60/40.

Physical Properties of Cyclic Olefin Thermoplastics

The preferred molecular weight of the cyclic olefin thermoplastic resin to be used in the present invention is appropriately selected depending on the application. The weight average molecular weight of polystyrene in terms of gel permeation chromatography (GPC) is 1 × 10 ³ to 1 × 10 ⁶ . It is preferable and it is more preferable that it is 1 * 10 <^4> -5 * 10 <^5> . If the molecular weight is too small, the mechanical strength may be insufficient, and even if the molecular weight is too high, the solution viscosity and the melt viscosity may be too high, resulting in problems in workability. In the said range, both strength and workability are excellent.

As glass transition temperature (Tg) of the cyclic olefin thermoplastic resin used for this invention, it is 120 degreeC or more, Preferably it is 120-300 degreeC, More preferably, it is 120-250 degreeC. When Tg is less than 120 degreeC, thermal deformation may arise in the film or sheet | seat obtained, for example, in the use required for heat resistance, such as a vehicle mounting use, and may become a problem. On the other hand, when Tg exceeds 300 degreeC, melt extrusion process becomes difficult or it is unpreferable since the possibility of resin deterioration by the heat at the time of such processing increases.

The copolymer used in the present invention preferably has a light transmittance of 80% or more at a wavelength of 400 nm in the film having a thickness of 100 μm, more preferably 85% or more. When the light transmittance at wavelength 400nm is less than the said range, when the transparent composite composition of this invention is used as a plastic substrate for display elements, display performance may be inadequate.

For the optical anisotropy of the film having a thickness of 100 ㎛ of the copolymer used in the present invention, Equation (1), the incident angle 0 ° and the retardation Re _0, Re preferably not more than ₄₅ is 20 nm in the 45 ° shown by 2 It is more preferable that it is 10 nm or less. If the retardation exceeds 20 nm, the optical anisotropy is large and the display performance is insufficient.

Re ₀ = (n _X -n _Y ) × d

Wherein, Re ₀ is the retardation time with respect to the three-dimensional coordinates X, Y, Z of the film viewed from the front side (Z-axis coordinate), n _X, n _Y is the refractive index in the X axis direction, Y axis direction, d Is the optical path length.

Re ₄₅ = (n _a -n _b ) × d '

In the formula, Re ₄₅ is a retardation when the viewing angle is inclined 45 ° from the Z axis to the X axis with respect to the three-dimensional coordinates X, Y, and Z of the film, n _a , n _b are the major axis directions of the refractive index ellipsoid, It is the refractive index of a short axis direction, and d 'is the optical path length.

The retardation Re ₀ and Re ₄₅ is determined by the structure of the polymer and its molding method and conditions, and can be controlled to some extent by the molding method and conditions, but basically the structure of the polymer is dominant, The coalescence can be said to be a structure with a small retardation.

Method for producing cyclic olefin thermoplastic resin

The resin of the present invention is mainly produced by ring-opening polymerization and preferably hydrogenation of a specific monomer and, if necessary, a copolymerizable monomer in the presence of a catalyst in a soluble solvent.

<Opening polymerization catalyst>

In the present invention, the ring-opening polymerization reaction for obtaining (1) the ring-opening polymer of the specific monomer and (2) the ring-opening copolymer of the specific monomer and the copolymerizable monomer is carried out in the presence of a metathesis catalyst.

This metathesis catalyst comprises (a) at least one selected from the compounds of W, Mo, and Re, (b) a periodic table of Deming group IA elements (e.g., Li, Na, K, etc.), IIA group elements (e.g., For example, Mg, Ca, etc., group IIB elements (e.g., Zn, Cd, Hg, etc.), group IIIA elements (e.g., B, Al, etc.), group IVA elements (e.g., Si, Sn, Pb, etc.), or a compound of a group IVB element (e.g., Ti, Zr, etc.) and comprising a combination with one or more selected from those having one or more of the above element-carbon bonds or the element-hydrogen bonds to be. In this case, in order to increase the activity of the catalyst, the (c) additive described later may be added.

Representative examples of the compound of W, Mo or Re suitable as the component (a) include WCl ₆ , MoCl ₆ , and ReOCl _3. The compound described in Unexamined-Japanese-Patent No. 1-32626 No. 8th page left lower row 6th-8th page upper right upper 17th row is mentioned.

(b) Specific examples of the component _{nC 4 H 9 Li, (C} 2 H 5) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1 .5, (C 2 H 5) AlCl ₂ , methylalumoxane, LiH, etc. The compound described in Unexamined-Japanese-Patent No. 1-32626 8th upper right row 18th to 8th lower right third row is mentioned.

As representative examples of the component (c), which is an additive, alcohols, aldehydes, ketones, amines, and the like can be preferably used, but also, in Japanese Patent Laid-Open No. Hei 1-32626, page 8, right bottom 16th to ninth page The compound described in the upper left line 17 can also be used.

As the usage-amount of a metathesis catalyst, in the molar ratio of the said (a) component and a specific monomer, "(a) component: specific monomer" is a range which usually becomes 1: 500-1: 50,000, Preferably it is 1: 1,000-1: 10 , O00.

The ratio of component (a) and component (b) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30, in terms of metal atomic ratio (a) :( b).

The ratio of the component (a) and the component (c) is in a molar ratio of (c) :( a) in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1.

<Polymerization Solvent>

As a solvent (solvent constituting a molecular weight regulator solution, a solvent of a specific monomer and / or metathesis catalyst) used in the ring-opening polymerization reaction, for example, alkanes such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, Cycloalkanes such as cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, Halogenated alkanes such as chlorobenzene, chloroform and tetrachloroethylene, compounds such as aryl halide, saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate and dimethoxyethane, dibutyl ether, Ethers, such as tetrahydrofuran and dimethoxyethane, etc. are mentioned, These can be used individually or in mixture. Of these, aromatic hydrocarbons are preferred.

As a usage-amount of a solvent, "a solvent: specific monomer (weight ratio)" is the quantity which is usually 1: 1-10: 1, Preferably it is the quantity which is 1: 1-5: 1.

<Molecular weight regulator>

Although molecular weight control of the ring-opening (co) polymer obtained can be performed also by polymerization temperature, the kind of catalyst, and the kind of solvent, in this invention, it adjusts by coexisting a molecular weight modifier in a reaction system.

Here, as a preferable molecular weight modifier, alpha olefins and styrene, such as ethylene, a propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Among these, 1-butene and 1-hexene are especially preferable.

These molecular weight modifiers can be used individually or in mixture of 2 or more types.

As a usage-amount of a molecular weight modifier, it is 0.005-0.6 mol, Preferably it is 0.02-0.5 mol with respect to 1 mol of specific monomers used for ring-opening polymerization reaction.

<Hydrogenated Catalyst>

In the hydrogenation reaction, a hydrogenation catalyst is added to a conventional method, that is, a ring-opening polymer solution, and hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm is 0 to 200 캜, preferably 20 to 180 It is carried out by acting at 占 폚.

As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are mentioned.

As a heterogeneous catalyst, the solid catalyst which supported noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. As the homogeneous catalyst, naphthenate nickel / triethylaluminum, nickelacetylacetonato / triethylaluminum, cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (tri Phenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or granular.

These hydrogenated catalysts are used in a ratio such that the ring-opening (co) polymer: hydrogenated catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.

Thus, the hydrogenated (co) polymer obtained by hydrogenation has the outstanding thermal stability, and the characteristic does not deteriorate also by the heating at the time of shaping | molding process or the use as a product.

The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 400 MHz and ¹ H-NMR. . The higher the hydrogenation rate, the better the stability against heat and light.

In this invention, it is preferable that the gel content contained in the ring-opening (co) polymer used as a cyclic olefin thermoplastic resin or its hydrogenated substance is 5 weight% or less, and it is especially preferable that it is 1 weight% or less.

The transparent composite of the present invention is composed of glass fiber cloth together with the cyclic olefin thermoplastic resin.

[Glass fiber cloth]

Although the refractive index of glass fiber cloth is not specifically limited, It is preferable to exist in the range of 1.50-1.57 in consideration of the refractive index of the said cyclic olefin thermoplastic resin.

Although glass fiber, a glass cross, a glass nonwoven fabric, etc. are mentioned as a glass fiber cloth used by this invention, Glass cross is especially preferable from the effect of reducing a linear expansion coefficient, and optical isotropy.

Examples of the glass include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, low dielectric constant glass, high dielectric constant glass, and the like, but less ionic impurities such as alkali metals are available. Easy E glass, S glass, and NE glass are preferable.

When using a glass cross as a glass fiber cloth, there is no restriction | limiting in particular in the weaving method, Plain weave, twill, runner weave, yarn weave, a woolen weave, etc. can be applied, Especially, a plain weave is preferable.

It is preferable that it is 15-200 micrometers normally, and, as for the thickness of a glass cross, it is more preferable that it is 15-100 micrometers. Only one piece of glass cross may be sufficient, and multiple sheets may be used overlapping.

In order to improve the adhesiveness between the glass fiber cloth and the cyclic olefin thermoplastic resin, the surface of the glass fiber cloth is silane coupling agent such as aminosilane, styrylsilane, epoxysilane, methacryloxysilane, acryloxysilane, vinyl silane, aluminum chelate compound, or the like. Treated with a metal chelate compound. If such a surface treatment is performed, the adhesion between the glass fiber cloth and the cyclic olefin thermoplastic resin is increased, so that the transparency of the sheet containing the transparent composite can be increased, and the surface of the glass fiber cloth generated when the sheet is repeatedly subjected to bending. It is possible to suppress the drop in transparency due to the interface peeling between the polymer and the polymer.

[Transparent complex]

The transparent composite of this invention consists of said cyclic olefin thermoplastic resin and glass fiber cloth.

The light transmittance at a wavelength of 400 nm of the transparent composite is 80% or more, preferably 85% or more. What has such a light transmittance is high transparency. In order to make the light transmittance at a wavelength of 400 nm to 80% or more, it is necessary to adjust the refractive index difference between the cyclic olefin thermoplastic resin and the glass fiber cloth to within 0.01, and change the composition of the cyclic olefin thermoplastic resin to match the refractive index of the glass fiber cloth, Any adjustment method using the glass fiber cloth which matches the refractive index of a cyclic olefin thermoplastic resin can be taken.

0.01 or less are preferable and, as for the refractive index difference of a cyclic olefin thermoplastic resin and glass fiber cloth, 0.005 or less are more preferable. When the refractive index difference exceeds 0.01, the transparency of the obtained transparent composite composition may be inferior.

In the transparent composite of the present invention, thermoplastic or thermosetting oligomers or polymers may be used in combination, if necessary, within a range that does not impair transparency, heat resistance, non-coloring properties or mechanical properties. Moreover, antioxidant, ultraviolet absorber, antistatic agent, dye, pigment, etc. can also be mix | blended as needed.

It is preferable that the average linear expansion coefficient in 50-140 degreeC of the transparent composite in this invention is 60 ppm / degrees C or less. If it exists in this range, since the dimensional stability with respect to the temperature of a transparent composite is high and there is little optical anisotropy, it becomes suitable for glass replacement use.

1-90 weight% is preferable and, as for the compounding quantity of the glass fiber cloth in a transparent composite_body | complex, 10-70 weight% is more preferable. If the blending amount of glass fiber cloth is less than the lower limit, the effect of low linear expansion due to complexation is not observed. If the glass fiber cloth exceeds the upper limit, the mechanical strength is drastically deteriorated. You may not be able to plan.

The transparent composite according to the present invention is preferable in the case of a sheet having a thickness of 20 to 2000 µm in terms of strength, weight reduction, solvent resistance, and the like.

[Method for Producing Transparent Composite]

The transparent composite of the present invention typically has the shape of a film, sheet or the like. As the molding method of the transparent composite of the present invention, the glass fiber cloth, preferably glass cross, is immersed in a solution in which the cyclic olefin thermoplastic resin is dissolved, and then dried at, for example, room temperature to 200 ° C,

The obtained surface-treated glass fiber cloth is sandwiched between two sheets each having a thickness of 20 to 1000 µm, usually containing the cyclic olefin thermoplastic resin, and preferably heat compression molded at 200 to 300 ° C. The sheet containing the cyclic olefin thermoplastic resin can be produced by a known method, for example, a casting method or the like is employed.

Alternatively, the glass fiber cloth can be immersed in the cyclic olefin thermoplastic resin solution, rolled between metal rolls, and dried, for example, at 150 to 300 ° C. to obtain a transparent composite, and on one side or both sides of the sheet. After apply | coating the said cyclic olefin thermoplastic resin solution, the method of drying at 150-300 degreeC and manufacturing a transparent sheet, etc. can also be employ | adopted, for example.

If necessary, the glass fiber cloth may be immersed in the cyclic olefin thermoplastic resin solution and rolled between metal rolls, and then the drying operation may be repeated a plurality of times.

It is preferable that it is 3-50 weight% normally, and, as for solid content concentration of the cyclic olefin thermoplastic resin solution used for manufacture of such a transparent composite_body | complex, it is more preferable that it is 3-30 weight%.

As described above, the glass fiber cloth is a solution containing a silane coupling agent such as aminosilane, styrylsilane, epoxysilane, methacryloxysilane, acryloxysilane, vinyl silane or a metal chelate compound, or a cyclic olefin thermoplastic resin. It may be processed. As a process, after immersing glass fiber cloth in the solution which melt | dissolved, it is preferable to dry at the temperature of 150-300 degreeC. Although it does not restrict | limit especially as a density | concentration at this time, In the case of containing a silane coupling agent and a metal chelate compound, when it contains a cyclic olefin type thermoplastic resin, it shall be 3 to 50 weight% of processing conditions, It is preferable at the point of processing efficiency.

When such a film is processed into a desired shape, an optical sheet such as a liquid crystal display substrate, an organic EL display element substrate, a color filter substrate, a touch panel substrate, a solar cell substrate, a transparent plate, an optical lens, an optical element, an optical waveguide, It can use suitably as glass replacement materials, such as an LED sealing material.

<Example>

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, it is not limited to the following example.

In addition, the various measuring methods in an Example are as follows.

(1) Copolymer Composition: 10 mg of the copolymer was placed in a 5 mmΦ tube, dissolved in a deuterated chloroform solvent, diluted to a liquid level of 4 cm, and subjected to 270 by ¹ H-NMR (manufactured by Nippon Denshi, EX-270). Measured at MHz and obtained from absorption ratio of protons.

(2) Weight average molecular weight (in terms of polystyrene) by GPC: 0.5 g of a cyclic olefin thermoplastic resin was dissolved in 100 cc of tetrahydrofuran using GPC and HLC8010 manufactured by Tosoh Corporation to prepare a sample, and standard polystyrene was manufactured by Tosoh Corporation. Measured using standard polystyrene.

(3) Glass transition temperature (Tg): It measured at the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter DSC6200 by Seiko Instruments.

(4) Pyrolysis start temperature (Td ₀ ): It measured at 20 degree-C / min in air using TG-DTA DTG60 by Seiko Instruments.

(5) Transparency (spectral light transmittance): The film (100 micrometers in thickness) containing the casting film (100 micrometers in thickness) of the cyclic olefin thermoplastic resin of this invention, and a transparent composite composition was produced by the following method, and visible and ultraviolet light was produced. The light transmittance at wavelength 400 and 550 nm was calculated | required by the spectrophotometer (The Hitachi U-2010 Spectro Photo meter).

(Casting film production method of cyclic olefin thermoplastic resin)

The cast film of the cyclic olefin thermoplastic resin bonded to the glass cross is cast on a commercially available polyester film (hereinafter referred to as PET film) by casting a resin solution (solid content concentration 20 wt%), and dried at room temperature overnight, and then PET The film was peeled off and dried at 120 ° C. for 2 hours to obtain a cast film having a thickness of about 80 μm.

(Film Production Method of Transparent Composite Composition)

A commercially available glass cross (already surface treated) is immersed in the cyclic olefin thermoplastic resin solution of the present invention and dried at room temperature to 200 ° C., and then the casting film having a thickness of 10 to 100 μm comprising the cyclic olefin thermoplastic resin of the present invention. (Room temperature dry goods) was sandwiched up and down, and heat compression molding at 200-300 degreeC, and the film of about 80 micrometers in thickness was obtained.

<Evaluation>

(1) refractive index:

Using the obtained film (80 micrometers in thickness), the total reflection angle was measured using the refractive index and film thickness measuring apparatus "MODEL 2010 PRISM COUPLER" manufactured by Metricon Corp., and the refractive index of the material was calculated | required. At this time, and the refractive index at a wavelength of 589 nm (D line), 20 ℃ with n _D ^20.

(2) Optical Anisotropy (Re ₀ , Re ₄₅ ):

A He-Ne laser (λ = 632.8 nm) was used as a light source at an incident angle of 0 ° and 45 ° by means of a rotating analyzer automatic ellipsometer manufactured by Mizoshi Kogyo Kogyo Co., Ltd., using the obtained film (thickness: 80 μm). Measured using.

(3) linear expansion coefficient:

Using a TMA (Thermal mechanical Analysis) SS6100 (manufactured by Seiko Instruments, Inc.), a film piece having a sample shape of 80 μm in thickness, 10 mm in length, and 10 mm in width is fixed upright, and a load of 1 g weight is applied by a probe. Was added. In order to remove the thermal history of the film, the temperature was once elevated to 5 ° C./min from room temperature to 140 ° C., and then again at a rate of 5 ° C./min from room temperature, and the linear expansion coefficient was determined from the elongation gradient of the film piece between 50 and 140 ° C. Obtained.

(4) Tensile strength and elongation:

In accordance with JIS K7113, the test piece was measured at a tensile speed of 3 mm / minute.

<Polymerization Example 1>

250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (monomer A), 18 parts of 1-hexene (molecular weight regulator), toluene 750 parts were put into the reaction vessel which carried out the nitrogen substitution, and this solution was heated to 60 degreeC. Then, 0.62 parts of toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten chloride (t-butanol: methanol: tungsten = 0.35 mol: 0.3) modified with t-butanol and methanol were added to the solution in the reaction vessel. 3.7 parts of toluene solution (concentration 0.05 mol / L) of the mole: 1 mol) was added, and the ring-opening copolymer solution was obtained by heating and stirring this system at 80 degreeC for 3 hours. The polymerization conversion rate in this polymerization reaction was 97%.

4,000 parts of the ring-opening copolymer solution thus obtained were put into an autoclave, and 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening copolymer solution, and the hydrogen gas pressure was 100 kg / cm ² , Hydrogenation was performed by heat-stirring for 3 hours on conditions of reaction temperature of 160 degreeC.

After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was discharged. The reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated thermoplastic norbornene-based resin.

The hydrogenation rate of the thermoplastic norbornene-based resin (hereinafter referred to as "resin A") thus obtained was measured by 270 MHz ¹ H-NMR and found to be 99.9%.

Tg of resin A was 168 degreeC. Moreover, when the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion were measured by GPC method (solvent: tetrahydrofuran), Mn is 34,000, Mw is 119,000, molecular weight distribution (Mw / Mn) is 3.5 It was.

<Polymerization Example 2>

225 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (monomer A) and bicyclo [2.2.1] hept-2-ene (Monomer B) Except having used the 1-hexene amount in 10 parts using 25 parts, it carried out similarly to the polymerization example 1, and obtained the hydrogenated thermoplastic norbornene-type resin (henceforth "resin B"). The hydrogenation rate was measured using 270 MHz ¹ H-NMR and found to be 99.9%. In addition, 270 MHz ¹ H-NMR was measured using the ratio of a structural unit derived from a monomer B b was 7.3%. Here, the ratio of the structural unit b is the proton absorption of methyl of the methyl ester of the structural unit a derived from the monomer A appearing at about 3.7 ppm and the protons of the alicyclic structures of the structural units a and b appearing at 0.15 to 3 ppm. Calculated from absorption.

Tg of resin B was 137 degreeC. In addition, similarly to the polymerization example 1, Mn of polystyrene conversion measured by GPC method was 34,000, Mw was 120,000, and molecular weight distribution (Mw / Mn) was 3.53.

<Polymerization Example 3>

170 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (monomer A) and bicyclo [2.2.1] hept-2-ene (Monomer B) A thermoplastic norbornene-based resin (hereinafter referred to as "resin C") which was hydrogenated was obtained in the same manner as in Polymerization Example 1 except that 80 parts were used and 1-hexene amount was 7 parts. 270 MHz ¹ H-NMR was measured using the hydrogenation ratio was 99.9%. In addition, 270 MHz ¹ H-NMR was measured using the ratio of a structural unit derived from a monomer B b was 23.3%. Here, the ratio of the structural unit b is the proton absorption of methyl of the methyl ester of the structural unit a derived from the monomer A appearing at about 3.7 ppm and the protons of the alicyclic structures of the structural units a and b appearing at 0.15 to 3 ppm. Calculated from absorption.

Tg of resin C was 102 degreeC. In the same manner as in Polymerization Example 1, Mn of polystyrene conversion measured by GPC method was 29,000, Mw was 105,000, and molecular weight distribution (Mw / Mn) was 3.62.

<Example 1>

NE glass cross (thickness 30 µm, plain weave, refractive index = 1.509, manufactured by Nittobo, surface treated) was immersed in the toluene solution (solid content concentration 20 wt%) of the resin A of <polymerization example 1>, followed by 1 at 120 ° C. Dried over time.

On the other hand, the toluene solution (solid content concentration 20 wt%) of the resin A of <polymerization example 1> was cast on a commercially available PET film using an applicator, dried at room temperature for 1 day, and then peeled from the PET film, followed by 130 ° C. It dried for 1 hour, and obtained the film of about 50 micrometers in thickness. Thereafter, the treated NE glass cross was sandwiched by two casting films of upper and lower sides (polymer film / treated NE glass cross / polymer film), and heat compression molding was performed at 250 ° C. to prepare a film having a thickness of about 80 μm. .

<Example 2>

A film having a thickness of about 80 μm was produced in the same manner as in Example 1 except that the NE glass cross having a thickness of 30 μm in Example 1 was not used and a NE glass cross having a thickness of 50 μm was used instead.

<Example 3>

NE glass cross (thickness 30 μm, plain weave, refractive index = 1.509, manufactured by Nittobo, surface treated) was immersed in a toluene solution (solid content concentration of 20% by weight) of resin B of <polymerization example 2>, followed by 1 at 120 ° C. Dried over time.

On the other hand, the toluene solution (solid content concentration 20 wt%) of the resin B of <polymerization example 2> was cast on a commercially available PET film using an applicator, dried at room temperature for 1 day, and then peeled from the PET film, followed by 100 ° C. It dried for 1 hour, and obtained the film of about 50 micrometers in thickness.

Thereafter, the treated NE glass cross was sandwiched by two casting films of upper and lower sides (polymer film / treated NE glass cross / polymer film), and heat compression molding was performed at 250 ° C. to prepare a film having a thickness of about 80 μm. .

Comparative Example 1

In Example 1, the toluene solution (solid content concentration 20 weight%) of resin A of the said <polymerization example 1> was marketed, without using NE glass cross (thickness 30 micrometers, plain weave, refractive index = 1.509, the product made by Nittobo). Cast using an applicator on the PET film, dried at room temperature for 1 day and then peeled from the PET film, and then dried stepwise at 120 ° C. for 2 hours, 150 ° C. for 2 hours, and 170 ° C. for 2 hours to have a thickness of about 80 μm. Film was prepared.

Comparative Example 2

NE glass cross (thickness 30 μm, plain weave, refractive index = 1.509, manufactured by Nittobo, surface treated) was immersed in a toluene solution (solid content concentration 20 wt%) of resin C of <polymerization example 3>, followed by 1 at 120 ° C. Dried over time.

On the other hand, the toluene solution (solid content concentration 20 wt%) of the resin C of <polymerization example 3> was cast on a commercially available PET film using an applicator, dried at room temperature for 1 day, and then peeled from the PET film, followed by 100 ° C. It dried for 1 hour, and obtained the film of about 50 micrometers in thickness.

Thereafter, the treated NE glass cross was sandwiched by two casting films of upper and lower sides (polymer film / treated NE glass cross / polymer film), and heat compression molding was performed at 250 ° C. to prepare a film having a thickness of about 80 μm. .

Comparative Example 3

In Example 1, NE glass cross (thickness 30 micrometers, plain weave, refractive index = 1.509, manufactured by Nittobo) was not used, and instead, E glass cross (50 micrometers thick, plain weave, refractive index = 1.560, manufactured by Unichika) was used. A film having a thickness of about 80 μm was obtained in the same manner as in Example 1 except for using.

All results are shown in Table 1 below.

Note 1) It is difficult to obtain the coefficient of linear expansion due to shrinkage of the film.

    * 2) The measurement is not performed because the film is opaque.

According to the present invention, a transparent composite having colorlessness, excellent transparency and heat resistance, small optical anisotropy, small linear expansion coefficient, and low optical anisotropy can be obtained.

Such a transparent composite material is preferably used for liquid crystal display substrates, organic EL display element substrates, color filter substrates, touch panel substrates, optical sheets such as solar cell substrates, transparent plates, optical lenses, optical elements, optical waveguides, LED sealing materials and the like. Can be used.

Claims (6)

[A] cyclic olefin thermoplastic resin [B] fiberglass cloth Transparent composite, characterized in that it contains. The cyclic olefin thermoplastic resin of claim 1, [A1] Ring-opening polymer of one or more monomers represented by the following formula (1); [A2] Ring-opening copolymer with a monomer copolymerizable with at least one monomer represented by the following formula (1); And [A3] A (co) polymer formed by hydrogenating a ring-opening polymer [A1] or a ring-opening copolymer [A2] Transparent composite containing at least one of. <Formula 1>

(Wherein^One To R⁴Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 30 carbon atoms, or other monovalent organic group, and may each be the same or different, and R^OneAnd R² Or R³And R⁴May be integrated to form a divalent hydrocarbon group, and R^OneOr R²And R³ Or R⁴May be bonded to each other to form a monocyclic or polycyclic structure, m is 0 or a positive integer, p is 0 or a positive integer, when m is 0, p is also 0) The transparent composite of claim 1, wherein the glass fiber cloth is a glass cross. The glass fiber cloth is dried, after immersing a glass fiber cloth in the solution (solid content concentration 3-50 weight%) in which the cyclic olefin thermoplastic resin melt | dissolved, and drying. The glass fiber cloth is immersed in a solution (solid content concentration of 3 to 50% by weight) in which the cyclic olefin thermoplastic resin is dissolved, and then dried, and the obtained surface-treated glass fiber cloth is sandwiched between two sheets containing the cyclic olefin thermoplastic resin. Method for producing a transparent composite, characterized in that the compression molding by heating. A glass fiber cloth is immersed in the solution (solid content concentration 3-50 weight%) in which the cyclic olefin thermoplastic resin melt | dissolved, and the said resin solution is apply | coated and dried on one side or both sides of the obtained surface-treated glass fiber cloth. Method for the preparation of a transparent composite.