JP2000147202A - Optical sheet made of transparent resin and optical parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical sheet which can be appropriately utilized for optical communication parts or a liquid crystal projector, a liquid crystal display or the like because it has superior molding workability, lightness, toughness and optical isotropy. SOLUTION: The optical sheet is a resin sheet of 0.2-1.5 mm thickness made of a transparent resin having >=80% visible radiation transmittance and >=150 deg.C glass transition temperature. The double refraction of the sheet is <=15 nm, the surface roughness Ra is <=0.1 μm and the impact resistance by the Dupont's falling ball impact test corresponds to >=600 gf.cm breaking energy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transparent resin optical sheet and an optical component. More specifically, the present invention relates to a transparent resin optical sheet and an optical component obtained by subjecting a transparent resin to a specific heat treatment. The optical component of the present invention can be manufactured by an efficient method, and the obtained product is lightweight and has excellent heat resistance, light resistance, and impact resistance. It has the advantage of being possible.

[0002]

2. Description of the Related Art In the past, inorganic glass was predominantly used as a material for producing products in the optical field. This is due to the excellent light transmittance, heat resistance, chemical resistance, water resistance, surface hardness, abrasion resistance,
This is due to characteristics such as a wide coefficient of linear expansion.

[0003] However, the above glass requires a polishing step, and when the surface is further subjected to fine processing, the processing itself requires a great deal of work. There was a problem that it was not suitable for. Further, low birefringence is required for some glass part applications, but in the case of glass parts, the required birefringence may not always be achieved.

Also, attempts have been made to apply to the field of optical components by using resins such as polymethyl acrylate, polycarbonate, polyarylate, and cyclic polyolefin, taking advantage of their properties and transparency. For example, development on an optical disk by reducing optical distortion is one example. As one of those attempts, development in fields requiring low birefringence, such as liquid crystal display substrates and liquid crystal projection optical components, has recently attracted attention. In these applications, the birefringence is 15 nm or less, preferably 10 nm or less, in a single-pass retardation value.
More preferably, it is required to be 5 nm or less, most preferably 2 nm or less. Furthermore, shape retention at 100 ° C. or higher is required due to various treatments or practical requirements.

As an attempt to solve the above problem, for example, Japanese Patent Application Laid-Open No. 60-222241 proposes a method of casting a heat-resistant resin such as polyethersulfone with a solvent. When the thickness exceeds 100 μm, it is industrially difficult to volatilize the solvent while maintaining the surface accuracy, and the liquid crystal display is used for the self-supporting property as a substrate or an optical component, or for securing the gas and water vapor barrier properties. A sheet or molded body having a thickness of more than 100 μm suitable for a substrate or an optical member could not be obtained.

On the other hand, in a method using thermoplastic molding such as extrusion molding or injection molding, optical distortion becomes large immediately after molding, and a molded article or sheet having desired quality is obtained in terms of optical characteristics. I could not do it. JP-A-7-1
No. 26375 proposes, as a method for eliminating optical distortion of a thermoplastically molded flat plate, a method in which a protective film is attached to an extruded plate and heated at normal pressure or higher to a glass transition temperature or higher.

[0007]

However, in the heat treatment at a temperature higher than the glass transition temperature, the freezing strain at the time of molding is eliminated with mechanical deformation. It is difficult to maintain the reproducibility with good reproducibility, and as a result, as shown in a comparative example described later, the optical distortion of the extruded flat plate cannot be eliminated, and on the optical characteristics, A substrate of the desired quality could not be obtained due to flatness accuracy. The purpose of the present invention is
An object of the present invention is to provide an optical sheet and an optical component having excellent productivity and having a required low birefringence value.

[0008]

The present inventors have made intensive studies in view of the above problems, and as a result, an optical sheet and an optical component obtained by performing a specific heat treatment on a specific material have a low birefringence value. They have found that they have sufficient properties as optical components, and have completed the present invention. That is, the gist of the present invention is a resin sheet having a thickness of 0.2 to 1.5 mm made of a transparent resin having a light transmittance of visible light of 80% or more and a glass transition temperature of 150 ° C. or more. Refraction is 1
An optical sheet made of a transparent resin, characterized by having a surface roughness Ra of 5 nm or less, a surface roughness Ra of 0.1 μm or less, and an impact strength by a DuPont dropping ball impact test of not less than 600 gf · cm of breaking energy value.

Further, another gist of the present invention is that a light transmittance by visible light is 80% or more and a glass transition temperature is 80%.
An optical component made of a transparent resin having a temperature of not less than 0 ° C. and having a birefringence of 15 nm or less and a surface roughness Ra of 0.1 μm or less.
The optical sheet and optical component of the present invention can be used in any shape, and are applied to optical communication components such as optical amplifiers, optical waveguides, and optical fibers, nonlinear optical elements, lenses, dark fluorescent materials, and the like. You. Further, since the raw material resin used in the present invention has a good light transmittance in a visible light region, it is also preferable to use it for a visible light lens or the like.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (Optical sheet) The transparent resin optical sheet of the present invention comprises:
A transparent resin having a visible light transmittance of 80% or more and a glass transition temperature of 150 ° C. or more is used. Further, the thickness of the sheet is 0.2 to 0.2 from the viewpoint of the stiffness of the sheet after hot pressing and the weight reduction of the resin substrate for a liquid crystal display element.
It is between 1.5 mm. The birefringence of the sheet is 15 nm
Hereinafter, the surface roughness Ra is 0.1 μm or less, and the impact strength according to the DuPont drop ball impact test is a fracture energy value of 600 gf · cm or more.

[0011] If the glass transition temperature of the resin is too low, the heat resistance required in the liquid crystal display element manufacturing process cannot be satisfied. About the glass transition temperature, from the necessity in the above manufacturing process, preferably 160 ° C. or more,
More preferably, the temperature is 170 ° C. or higher. If the thickness of the sheet (hereinafter sometimes referred to as a resin substrate) is too small, the gap between the substrates is kept constant when a product having an area exceeding 2 inches in diagonal line length is used for a liquid crystal display element. This is not preferable because color bleeding occurs.

Further, in addition to the lack of self-supporting property when the liquid crystal display element is enlarged, the gas barrier property of the substrate body is low, so that the liquid crystal sealed therein tends to be deteriorated during long-term use. In view of such a point, the thickness of the substrate is preferably at least 0.3 mm, more preferably at least 0.4 mm. On the other hand, if the thickness exceeds 1.5 mm, the advantage of reducing the weight of a standard 0.7 mm thick glass substrate is lost, which is not preferable. The upper limit of the thickness is more preferably 1.1 mm or less from this viewpoint.

The birefringence of a sheet refers to the in-plane birefringence between the film forming direction and the width direction of the sheet, and is represented by an optical phase difference in a single pass. If this birefringence value exceeds 15 nm in optical phase difference, problems such as color bleeding occur in the image quality when assembled into a liquid crystal display device. In order to obtain good image quality, the birefringence value is preferably 10 nm or less, more preferably 5 nm or less.

Regarding the surface roughness of the sheet, Ra is 0.1.
If it exceeds 1 μm, problems such as color bleeding will occur when assembled into a liquid crystal display element, and the image quality will deteriorate. In order to obtain good image quality, the thickness is preferably 0.05 μm or less, more preferably 0.01 μm or less. Regarding the impact strength, the problem of handling after assembling the liquid crystal display element, especially from the viewpoint of the difficulty of cracking when attached to a portable device, and the problem of the yield at the time of manufacturing the sheet or assembling the liquid crystal display element, Impact strength is 10cm x 10cm square size 0.2m by DuPont drop ball impact test
If the fracture energy value is less than 600 gf · cm in a test sample having a thickness of not less than m, problems such as a high possibility of breaking when dropped on a concrete floor occur, which is not preferable. This breaking energy value is preferably 900 gf · cm or more, more preferably 2000 gf · cm or more, and still more preferably 3000 gf · cm or more.
gf · cm or more, most preferably 10,000 gf · cm
That is all.

(Optical part) The optical part of the present invention is made of a transparent resin having a visible light transmittance of 80% or more and a glass transition temperature of 80 ° C. or more, and a birefringence of 15 nm.
Hereinafter, the surface roughness Ra is 0.1 μm or less.

The light transmittance of the above resin by visible light is preferably at least 85% and the glass transition temperature (Tg).
Is obtained by subjecting a transparent resin or a transparent resin processed body thereof preferably having a temperature of 120 ° C. or higher to a specific heat treatment. If the light transmittance of the resin is too low, when used as an optical member such as a resin substrate for a liquid crystal display element, a microlens array, or a diffraction grating, it is not appropriate due to problems such as a dark screen and a large loss of light amount. . If the glass transition temperature of the resin is too low, the heat resistance required in the manufacturing process of the liquid crystal display element cannot be satisfied,
Even when used as an optical member, it cannot withstand radiant heat due to irradiation from a light source.

The optical component of the present invention has the same light transmittance and Tg of visible light as the raw resin. Here, the optical components in the present invention include an optical filter, a polarizing plate, a retardation plate, a viewing angle control plate, a liquid crystal panel member such as a liquid crystal alignment film, an optical communication isolator, an electric advertising board, an illumination cover, and various windows. It means all materials that are irradiated, transmitted, and reflected such as materials.

Regarding the thickness of the optical component, it is distorted without self-supporting property and cannot function as an optical component. Therefore, the thickest portion is usually 0.2 mm or more, preferably 0.4 mm or more, more preferably Is desirably 1.0 mm or more. The birefringence, which indicates the optical distortion of an optical component, refers to the in-plane birefringence between the direction in which the resin is formed and the direction perpendicular thereto, and is expressed by an optical phase difference. If the optical retardation exceeds 15 nm, sufficient characteristics cannot be obtained when used as an optical component. Therefore, the birefringence value is preferably 10 nm or less, more preferably 5 n.
m or less is desirable.

The surface roughness Ra of the optical component is usually 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.01 μm or less, in order to obtain good characteristics. Regarding the impact strength, in particular, from the viewpoint of resistance to cracking when used in a portable device, the impact strength is usually 600 gf · c in a test sample having a thickness of 1 mm according to the DuPont impact test.
m or more, preferably 900 gf · cm or more, more preferably 2000 gf · cm or more, and most preferably 300 gf · cm or more.
0 gf · cm or more is desirable.

(Raw material resin) As described above, the resin used for the optical sheet and optical component of the present invention has a specific visible light ray transmittance and a glass transition temperature. As a transparent resin having characteristics,
Polycarbonate, polyester carbonate, aromatic polyester, polysulfone, polyethersulfone,
In addition to a non-crystalline resin such as a cyclic polyolefin, various epoxy-based, diacrylate-based, dimethacrylate-based curable resins by heat or light can be used.

Among these resins, a thermoplastic resin is particularly preferably used from the viewpoint of ensuring impact resistance without deteriorating the characteristics of birefringence and surface roughness. In addition, among various thermoplastic resins, polycarbonate resin with excellent impact resistance,
Alternatively, a polyester carbonate resin is suitably used. Among them, in addition to light transmittance by visible light, which is a characteristic as an optical sheet and an optical component, in addition to a glass transition temperature,
In order to ensure the impact strength without lowering the birefringence and surface roughness characteristics, the carbonate bond unit having a cyclic aliphatic group having excellent impact strength corresponding to the melt fluidity is used for all the carbonate bond units. A polycarbonate resin or a polyester carbonate resin containing at least 5 mol%, preferably at least 15 mol%, more preferably at least 25 mol% is preferably used.

Furthermore, among the polycarbonate resins, the cyclic aliphatic group contained in the carbonate binding unit is 1,1-
Those introduced from bis (4-hydroxyphenyl) cyclohexane (commonly known as bisphenol Z) are preferably used. The reason is that since a bulky functional group enters a methylene bond between two benzene rings, the movement of the molecular chain in this portion is regulated, a high Tg is obtained, and further, the orientation is disturbed, and intrinsic birefringence and This is to reduce the photoelastic coefficient. Furthermore, when the bulky functional unit is aromatic, a stack of benzene rings may be generated and the intrinsic birefringence may be reduced, but the orientation may not be disturbed and the total birefringence may not be reduced. And, as a result, the occurrence of crystallization, cracks and crazes due to the solvent may be promoted. Therefore, those containing a functional unit introduced from the cycloaliphatic unit are preferably used.

In the present invention, a transparent resin having a viscosity average molecular weight of 10,000 to 25,000 is preferably used. Since it is difficult to relax the orientation, the birefringence value does not reach the required value. Considering such properties, the viscosity average molecular weight is preferably
11000 to 22000, more preferably 12000 to 12000
18000 is preferably used.

The above polycarbonate resin comprises a specific dihydric phenol compound and a carbonate precursor such as phosgene or a carbonic acid diester as main components and, if necessary, reacts with a terminal terminator to form an interfacial polymerization method or a melt polymerization method. Can be obtained by If necessary, a trivalent or higher bisphenol may be copolymerized in an appropriate amount, and the main chain of the polymer may be linear or branched. Furthermore, aromatic dicarboxylic acid derivatives as raw materials,
An aromatic polyester carbonate resin can be obtained by adding an aromatic monocarboxylic acid derivative.

The above dihydric phenol compounds include:
1,1-bis (4-hydroxyphenyl) cyclohexane (commonly known as bisphenol Z), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1
-Bis (3,5-dimethyl-4-hydroxyphenyl)
Cyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-
Isobutyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-difluoro-4-hydrochitophenyl) cyclohexane,
Bisphenols which are cyclohexane derivatives such as 1-bis (3-chloro-4-hydroxyphenyl) cyclohexane and 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4- (Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1-bis (3-ethyl-4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) -3,
3,5-trimethylcyclohexane, 1,1-bis (3
-Fluoro-4-hydroxyphenyl) -3,3,5-
Bisphenols which are 3,3,5-trimethylcyclohexane derivatives such as trimethylcyclohexane and 1,1-bis (3,5-difluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are exemplified. These may be a mixture of two or more.

As the copolymerization component together with the above dihydric phenol compound, for example, 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), bis (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4
-Hydroxyphenyl) -n-propane, 1,1-bis (4-hydroxyphenyl) -n-butane, 1,1-bis (4-hydroxyphenyl) -n-pentane, 1,1
-Bis (4-hydroxyphenyl) -n-hexane,
1,1-bis (4-hydroxyphenyl) -n-heptane, 1,1-bis (4-hydroxyphenyl) -n-octane, 1,1-bis (4-hydroxyphenyl) -n
-Nonane, 1,1-bis (4-hydroxyphenyl)-
n-decane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) toluylmethane,
Bis (4-hydroxyphenyl)-(4-ethylphenyl) methane, bis (4-hydroxyphenyl)-(4-
n-propylphenyl) methane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (4-hydroxyphenyl)-(4-n-butylphenyl) methane, bis (4-hydroxyphenyl)-( 4
-Pentylphenyl) methane, bis (4-hydroxyphenyl)-(4-hexylphenyl) methane, bis (4
-Hydroxyphenyl)-(4-fluorophenyl) methane, bis (4-hydroxyphenyl)-(4-chlorophenyl) methane, bis (4-hydroxyphenyl)-
(2-fluorophenyl) methane, bis (4-hydroxyphenyl)-(2-chlorophenyl) methane, bis (4-hydroxyphenyl) tetrafluorophenylmethane, bis (4-hydroxyphenyl) tetrachlorophenylmethane, bis (3- Methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-ethyl-4-hydroxyphenyl) methane, bis (3-isobutyl-4-hydroxyphenyl) methane, Bis (3-t-butyl-4-
Hydroxyphenyl) -1-phenylmethane, bis (3
-Phenyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro-4-hydroxyphenyl) methane, bis (3-chloro-4- (Hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4) -Hydroxyphenyl) ethane, 1,1-bis (3-ethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) ethane, 1,1-bis (3-fluoro- 4-hydroxyphenyl) ethane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1-bis (3-chloro Bisphenols such as 4-hydroxyphenyl) ethane and 1,1-bis (3,5-dichloro-4-hydroxyphenyl) ethane in which a hydrogen atom is bonded to a central carbon, 2,2-bis (4-hydroxyphenyl) ) -N-butane, 2,2-bis (4-hydroxyphenyl) -n-pentane, 2,2-bis (4
-Hydroxyphenyl) -n-hexane, 2,2-bis (4-hydroxyphenyl) -n-heptane, 2,2-
Bis (4-hydroxyphenyl) -n-octane, 2,
2-bis (4-hydroxyphenyl) -n-nonane,
2,2-bis (4-hydroxyphenyl) -n-decane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (commonly known as bisphenol P), 1,1-bis (4-hydroxyphenyl)- 1-naphthylethane,
1,1-bis (4-hydroxyphenyl) -1-toluylethane, 1,1-bis (4-hydroxyphenyl)-
1- (4-ethylphenyl) ethane, 1,1-bis (4
-Hydroxyphenyl) -1- (4-n-propylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-isopropylphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) -1- (4-n-
Butylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-pentylphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1- (4-
Hexylphenyl) ethane, 1,1-bis (3-t-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-
(4-chlorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-
One at the central carbon such as (2-chlorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-tetrafluorophenylethane, and 1,1-bis (4-hydroxyphenyl) -1-tetrachlorophenylethane Bisphenols to which a methyl group is bonded, 2,2-bis (3
-Methyl-4-hydroxyphenyl) propane (commonly known as bisphenol C), 2,2-bis (3,5-dimethyl-
4-hydroxyphenyl) propane, 2,2-bis (3
-Ethyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-isobutyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane,
Bisphenols having two methyl groups bonded to a central carbon such as 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-methyl-
4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-t-butyl-4-hydroxyphenyl)
-1,1-diphenylmethane, bis (3-phenyl-4
-Hydroxyphenyl) -1,1-diphenylmethane,
Bis (3-chloro-4-hydroxyphenyl) -1,1
Bisphenols which are diphenylmethane derivatives such as -diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane (commonly known as bisphenol Z),
1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3
-Ethyl-4-hydroxyphenyl) cyclohexane,
1,1-bis (3-isobutyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4
-Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3 5-
Bisphenols which are cyclohexane derivatives such as dichloro-4-hydroxyphenyl) cyclohexane;
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-
4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3,5-dimethyl-4-
(Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3-isobutyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1
-Bis (3-fluoro-4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl)-
3,3,5 such as 3,3,5-trimethylcyclohexane
Bisphenols which are -trimethylcyclohexane derivatives, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-dimethyl −
4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene,
9,9-bis (3-isobutyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-fluoro-4-hydroxyphenyl) fluorene, 9,9-bis (3,5
Bisphenols which are fluorene derivatives such as -difluoro-4-hydroxyphenyl) fluorene;
Bis (4-hydroxyphenyl) cyclopentane, 1,
1-bis (4-hydroxyphenyl) cycloheptane,
Bisphenols which are cycloalkane derivatives such as 1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis (4-hydroxyphenyl) cyclononane, 1,1-bis (4-hydroxyphenyl) cyclodecane, Bisphenols to which an aromatic ring such as 4,4'-biphenol is directly bonded, bis (4-hydroxyphenyl)
Sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, bis (3-isobutyl-4) −
Hydroxyphenyl) sulfone, bis (3-fluoro-
Bisphenols which are sulfone derivatives such as 4-hydroxyphenyl) sulfone and bis (3,5-difluoro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) Ether, bis (3,5-dimethyl-
4-hydroxyphenyl) ether, bis (3-ethyl-4-hydroxyphenyl) ether, bis (3-isobutyl-4-hydroxyphenyl) ether, bis (3
Bisphenols having an ether bond such as -fluoro-4-hydroxyphenyl) ether and bis (3,5-difluoro-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4- (Hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, bis (3-isobutyl-4-hydroxyphenyl) sulfide, bis (3- Fluoro-4-hydroxyphenyl) sulfide, bis (3,5-difluoro-
Bisphenols having a sulfide bond such as 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) Sulfoxide, bis (3-
Ethyl-4-hydroxyphenyl) sulfoxide, bis (3-isobutyl-4-hydroxyphenyl) sulfoxide, bis (3-fluoro-4-hydroxyphenyl)
Bisphenols such as sulfoxide and bis (3,5-difluoro-4-hydroxyphenyl) sulfoxide; bisphenols such as bisphenols; bisphenols having a hetero atom-containing aliphatic ring such as phenolphthalein; dihydroxy such as hydroquinone, resorcinol and methylhydroquinone; Benzenes, dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene, bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) difluoromethane, 1,1
-Bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoroethane and 2,2-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoropropane One or more selected from bisphenols having no carbon-hydrogen bond can be used. The amount of the copolymer component used is selected from a range that does not impair the glass transition temperature (130 ° C. or higher) of the obtained polycarbonate resin.

The trihydric phenol to be copolymerized if necessary includes tris (4-hydroxyphenyl) methane,
1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1,
Compounds such as 3,5-tris (4'-hydroxyphenyl) benzene are used.

In the present invention, as the polycarbonate resin, a resin obtained by melting or blending a polycarbonate resin obtained from the above-mentioned dihydric phenol compound and a polycarbonate resin obtained from the above-mentioned bis compound as a copolymer component, as a melt or a solution. May be used. Phosgene should be as pure as possible.
Those containing no impurities such as carbon tetrachloride and methylene chloride are preferred.

Examples of the carbonic acid diester include bisalkyl carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, and the like, and bisaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and di-4-chlorophenyl carbonate. Activated carbonic acid derivatives such as phosgene, bromophosgene, bis (2,4,6-trichlorophenyl) carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate and carbodiimidazole; Phosgene oligomers such as triphosgene and trichloromethyl chloroformate, oligomers of aromatic polycarbonates having a terminal chloroformate group, terminal chloroformates Oligomers of aromatic polyester carbonates is illustrated having a group, is not particularly limited as long as having reactivity with bisphenols,
In the resin interfacial polymerization method or the pyridine method, a carbonate derivative having a highly active leaving group represented by phosgene is particularly preferably used, and in the melt polymerization method, a bisaryl carbonate such as diphenyl carbonate is particularly preferably used.

In the production of the polycarbonate resin of the present invention, an aromatic dicarboxylic acid derivative or a monocarboxylic acid having a hydroxyl group other than dihydric phenols, phosgene or carbonic acid diester, such as lactic acid and malic acid, may be copolymerized as an optional component. Can be used as an aromatic polyester carbonate. Further, a terminal terminator may be attached to the reaction components to adjust the molecular weight of the obtained resin.

The aromatic dicarboxylic acid derivative which may be used as a copolymer component of the aromatic polyester carbonate resin is an aromatic dicarboxylic acid or a compound in which one or both of its carboxyl groups are an ester, an acid halide or an acid anhydride. And a compound having condensation reactivity with a monomer represented by the general formula (A), which is a polymerization component of the resin, and a phenolic hydroxyl group contained in bisphenols. As the aromatic dicarboxylic acid, benzene derivatives such as terephthalic acid, isophthalic acid and phthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,
8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,4-naphthalenedicarboxylic acid, 2,5-
Examples include naphthalene derivatives such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Particularly preferred aromatic dicarboxylic acid derivatives include benzene derivatives such as terephthalic acid and isophthalic acid, aromatic dicarboxylic acids such as naphthalene derivatives such as 2,6-naphthalenedicarboxylic acid, and dimethyl esters and diacid chlorides thereof. No.

Examples of the aromatic monocarboxylic acid derivative having one phenolic hydroxyl group which may be used as a copolymer component of the aromatic polyester carbonate resin include p-hydroxybenzoic acid, m-hydroxybenzoic acid and o-hydroxybenzoic acid. Benzoic acid derivatives such as (salicylic acid);
Hydroxy-1-naphthalenedicarboxylic acid, 5-hydroxy-2-naphthalenedicarboxylic acid, 6-hydroxy-1
An aromatic monocarboxylic acid having one phenolic hydroxyl group such as a naphthalene carboxylic acid derivative such as -naphthalenedicarboxylic acid or 6-hydroxy-2-naphthalenedicarboxylic acid, or a phenolic hydroxyl group such as a methyl ester of the aromatic monocarboxylic acid. Examples thereof include an aromatic monocarboxylic acid ester having one, a compound in which a hydroxyl group contained in the aromatic monocarboxylic acid is acetylated, and the like. Of these, p-hydroxybenzoic acid and its methyl ester, or p-hydroxybenzoic acid derivatives such as acetylated p-hydroxybenzoic acid are most preferably used for reasons such as polymerization reactivity.

A compound having one phenolic hydroxyl group may be used as a terminal stopper. Examples of such a terminal stopper include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol,
2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 4-ethylphenol, 4-isopropylphenol, 4-n-propyl Phenol, 4-t-butylphenol, 4-isobutylphenol, 4-n-butylphenol, 4-
Monohydric phenols having an alkyl group, an aryl group, a halogen atom, and the like such as t-octylphenol, nonylphenol, 4-phenylphenol, tribromophenol, 4-dodecylphenol, and 4-stearylphenol are exemplified.

In the aromatic polyester carbonate resin, in addition to the compound having one phenolic hydroxyl group described in the preceding paragraph, aromatic monocarboxylic acids or The ester or acid halide may be used. Such aromatic monocarboxylic acids include benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid,
2,3-dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 2,5-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, 3,4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, 4- Ester benzoic acid, 4-isopropyl benzoic acid, 4-n-propyl benzoic acid, 4-t-butyl benzoic acid, 4-isobutyl benzoic acid, 4-n-butyl benzoic acid, 4-t-octyl benzoic acid, nonyl benzoic acid Acid, 4-
Representative examples thereof include benzoic acid derivatives having an alkyl group, an aryl group, a halogen atom and the like, such as phenylbenzoic acid, tribromobenzoic acid, 4-dodecylbenzoic acid, and 4-stearylbenzoic acid.

As a method for producing a polycarbonate resin, for example, (1) a method in which an alkali metal salt of a bisphenol and a carbonate derivative which is active against nucleophilic attack are used as raw materials, and an organic solvent dissolving a produced polymer and alkaline water are used. An interfacial polymerization method in which a polycondensation reaction is carried out at an interface, (2) a pyridine method in which a bisphenol compound and a carbonate derivative which is active against nucleophilic attack are used as raw materials, and a polycondensation reaction is carried out in an organic base such as pyridine; Any of the conventionally known methods such as a melt polymerization method of melt-polycondensation using a compound and a carbonate such as bisalkyl carbonate or bisaryl carbonate as raw materials may be applied. Further, the ratio of phosgene, alkali, amine catalyst and the like to bisphenols, the concentration of the reaction solution, the temperature and the reaction time may be arbitrarily set according to the purpose.

As a preferred embodiment of the raw material resin for the optical sheet of the present invention, a mixture of a polycarbonate resin having a carbonate bond having a carbonate bond having a cyclic aliphatic group and a polycarbonate resin having a general-purpose bisphenol A unit is provided. The mixing ratio is usually about 2: 8 to 8: 2 in weight ratio. (Manufacturing method of optical sheet and optical component) The optical sheet and optical component of the present invention can be obtained by subjecting the above transparent resin or its transparent resin processed body to hot pressing at the following temperature T.

[0037]

(Equation 4)

If T (° C.) shown in the above equation is too low, the effect of reducing birefringence is not sufficient, and a desired low retardation resin substrate may not be obtained. On the other hand, if it is too high, the industrial cycle time becomes longer, and problems such as deterioration of the resin may be caused. Hot press processing temperature T
(° C)

[0039]

(Equation 5)

It is desirable to carry out the hot pressing at a certain temperature. Regarding the upper limit temperature of the hot press processing temperature T (° C.),

[0041]

(Equation 6)

It is desirable to perform the hot pressing at a certain temperature. In the present invention, the heating / cooling time is not particularly limited, but it is industrially advantageous to shorten the heating / cooling cycle of the device as much as possible without impairing the temperature uniformity. In general, the heating time at the hot press temperature T is generally several seconds to one hour, preferably several seconds to 30 minutes,
More preferably, it is 1 to 20 minutes.

The heating rate up to the hot pressing temperature T is usually 5 to 70 ° C./min, preferably about 20 to 50 ° C./min. If the speed is too slow, the cycle time becomes longer, which causes a problem in industrialization. In addition, the time of exposure to a high temperature becomes longer, which may cause a problem of thermal deterioration. On the other hand, if too fast, uniform heating tends to be hindered.

The cooling rate from the hot press temperature T is usually about 5 to 50 ° C./min, preferably about 10 to 40 ° C./min. If the speed is too slow, the cycle time becomes longer, which causes a problem in industrialization. In addition, the time of exposure to a high temperature becomes longer, which may cause a problem of thermal deterioration. On the other hand, if the speed is too high, uniform cooling is hindered, and distortion due to cooling remains locally, which may adversely affect shape accuracy and birefringence.

Further, in heating and cooling, the temperature control accuracy of each part is extremely important. Within the effective range of the heating stage (pressing hot plate) of the press machine, if there is a temperature difference of 10 ° C or more at a certain moment during heating and cooling, the dimensional accuracy of the molded product will be impaired and warpage will occur. Or the birefringence may not be sufficiently reduced. As described above, it is desirable to use a high-precision press machine that can precisely and quickly control heating and cooling of the entire heating stage by circulating a heating medium as a heating press processing machine suitable for this application.

With respect to a method of molding a resin optical component to be subjected to hot pressing, a known extrusion molding method or injection molding method, such as extruding a molten resin from a die at a slit such as a T-die, casting a resin solution, or the like, What was produced by casting of a resin solution can be used. Among the above molding methods, the molecular weight suitable for molding, the strength of molecular orientation during molding, the removal of residual solvent, and the ease of transferability from the mold used during hot pressing, and ease of orientation relaxation In view of the above, as a molding method of a resin optical component, injection molding that does not use a solvent because the resin used has high fluidity is more desirable.

At the time of hot pressing, the surface roughness R of the portion constituting the plane of the surface to which the resin substrate is pressed and transferred from above and below is described.
a is preferably 0.1 μm or less. If this value is too large, for example, when assembled into a liquid crystal display element,
Problems such as color bleeding occur and image quality deteriorates. Further, when considered as an optical member, irregular reflection and scattering occur on the surface, and the optical characteristics deteriorate. In order to obtain good image quality and optical characteristics, the thickness is more preferably 0.05 μm or less, and further preferably 0.01 μm or less.

Press pressure P (g / c) during hot press processing
m ² ) is that the time average of the last one minute during which at least the hot pressing temperature T (° C.) is applied is 0 to 1000
(G / cm2). If this value is too small, the transfer accuracy from a flat surface may not be sufficient at the time of pressing, and if too large, the relaxation of the orientation of the resin becomes insufficient even if the pressing temperature is increased, and the birefringence value is set at the target. Is not reduced to In light of these points,

[0049]

Preferably, 10 ≦ P ≦ 500, more preferably, 20 ≦ P ≦ 200, and even more preferably, 40 ≦ P ≦ 100.

It is desirable to carry out the hot pressing at a certain pressure range. The atmosphere in which the hot pressing is performed is desirably an atmosphere of an inert gas such as nitrogen or argon or in a vacuum, and particularly preferably in a vacuum. When performed in normal air, the target substrate can be obtained without any problem by hot press treatment.However, due to the high temperature and oxygen in the air, the surface sandwiching the resin substrate surface and the resin processing body of the transfer medium from above and below can be obtained. It may be oxidized and difficult to peel off from the resin substrate. In particular, when this flat surface is reused many times, this phenomenon often occurs remarkably. Therefore, in the case where the process is carried out in an inert gas atmosphere, the oxygen gas concentration is desirably 10% by volume or less, preferably 5% by volume or less, more preferably 1% by volume or less, and most preferably 0.1% by volume or less.

Further, when the process is carried out in a vacuum, even if a gap is formed between the resin substrate and the flat surface, this portion does not remain as bubbles and remains more suitable as a manufacturing condition. Therefore, when the operation is performed in a vacuum, the pressure in the system is 10
0 mmHg or less, preferably 50 mmHg or less, more preferably 20 mmHg or less. In consideration of the points shown above, the hot press machine is equipped with a hot plate that has been subjected to high-precision surface finishing and a control system that enables accurate execution of a heating / cooling and pressure control and vacuum degree control program. A high-temperature tank-type vacuum hydraulic press is recommended. Temperature D after peeling from the surface sandwiching the resin substrate after hot pressing
(° C.) is the glass transition temperature Tg (° C.) of the raw resin,

[0052]

Tg> D ≧ Tg−120

It is preferred that If this temperature is too high, it may be deformed during peeling. If it is too low, the resin will crack due to the difference in linear expansion coefficient between the resin and the surface,
There is a risk of cracks. If it is within the range of the above formula, peeling from the surface of the resin can be performed without any problem.
Is

[0054]

[Mathematical formula-see original document] Preferably, Tg-20> D≥Tg-100, more preferably, Tg-40> D≥Tg-90, most preferably, Tg-40> D≥Tg-60.

It is desirable that These steps may be performed by a batch process, or may be a continuous process using, for example, a stainless steel belt or a turntable. The transparent resin optical sheet and optical component of the present invention are used for various display elements such as display, especially for liquid crystal display element, or for various optical members, especially for display-related, especially for liquid crystal projection optical parts and liquid crystal display. It can be suitably used as an optical sheet and an optical component used in a polarizing system such as a resin substrate for use.

[0056]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, the measuring method of various physical-property values is as follows. (1) Light transmittance (LT) Measured in accordance with JIS K7105. (2) Glass transition temperature Measured according to ASTM D3418.

(3) Thickness of Resin Molded Sheet The thickness of the sheet was measured with a thickness gauge. Unit: mm (4) Birefringence Automatic birefringence measurement base (Oak Seisakusho ADR-15)
0N) and the single-pass retardation value (R value, unit: nm) was measured by perpendicular incidence. (5) Surface roughness Surface roughness measuring device (Surfcom 575 manufactured by Tokyo Seimitsu Co., Ltd.)
Using A), the surface roughness (Ra, unit: μm) was measured with a diamond needle (1 μR, 90 ° cone), and the measurement length was 0.5 m.
m, cutoff value 0.16mm, measurement speed 0.06mm
/ Sec, measured under linear correction conditions.

(6) Impact strength test The impact strength test was measured by a DuPont dropping ball test. The measuring device used was a falling ball tester manufactured by Toyo Seiki Co., Ltd., and the lowest breaking energy value was represented by the lowest falling ball energy at which the sample to be measured was broken or cracked. (7) Type of base resin A resin having a structural formula shown in Table 2 was used. (8) Viscosity-average molecular weight For polycarbonate, the solution viscosity measured at 25 ° C. for a 6 g / L methylene chloride solution was determined by converting it to a Schnell viscosity equation.

(9) Damage Test An A5-sized resin substrate, which had been subjected to the press heat treatment, was naturally dropped on a concrete floor from a distance of 50 cm, and whether or not it was damaged was visually confirmed. (10) Preparation of chemical-resistant coating agent dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DCP-
A) 40 parts by weight, 25 parts by weight of epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayarad R130),
Dimethylolpropane tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DTMP-4)
A) 35 parts by weight, 2-hydroxy- as a photopolymerization initiator
5 parts by weight of 2-methyl-1-phenyl-propane-1 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 1800) is added, and the mixture is uniformly stirred and mixed under a nitrogen flow, and then defoamed to form a composition. I got something. This composition was uniformly applied on a target substrate by spin coating.

Example 1 Viscosity average molecular weight 14000, LT 85-90%, Tg1
A 0.8 mm thick, A5 size flat plate was molded by injection compression molding using a 200-ton injection machine (M-200B) manufactured by Meiki Seisakusho using 80 ° C polycarbonate P (see Table 2 for the structural formula). Subsequently, a hot press machine was previously heated to 100 ° C., and both surfaces of the obtained molded plate were sandwiched between stainless plates having a surface roughness Ra of 0.004 μm before absorbing moisture.
It heated to 10 degreeC over 10 minutes and performed press heat treatment. The pressing temperature was 270 ° C., the time was 20 minutes, and the pressure during pressing was 60 g / cm ² during the last 5 minutes at 270 ° C.

Thereafter, the mixture is cooled to 120 ° C. over 20 minutes,
Peeling from the stainless steel plate is performed when the temperature of the stainless steel plate is 12
When the temperature reached 0 ° C., the screwdriver was inserted between the stainless steel plates and peeled off, and the resin substrate adhered to one side of the stainless steel plate was slowly rolled up with a spatula-like material and peeled off. When an impact strength test was performed on the A5 size substrate peeled off at this stage, the substrate exhibited a minimum breaking energy value of 10,000 gf · cm or more.

Subsequently, after the substrate is degreased with ethanol,
The chemical resistance coating agent of the above (10) was coated on both sides by spin coating so as to have a thickness of 3 μm in a dry state.
The mixture was air-dried at room temperature for a minute, and was irradiated with ultraviolet rays from a 4 kW high-pressure mercury lamp at an irradiation amount of 6.0 J / cm ² to be cured. The irradiation unit used was "TOSCURE 40" manufactured by Toshiba Lighting & Technology Corporation. On the both surfaces of the obtained transparent substrate, as a gas barrier layer and an undercoat layer, SiOx is deposited to a thickness of 200 angstroms as a deposition material, and an ITO film is formed thereon by a sputtering process so as to have a thickness of 1000 angstroms. A film was formed.
When the surface roughness was measured at this stage, Ra = 0.004
μm. Further, the ITO transparent conductive film was patterned with a resist to form a transparent conductive wiring, and then a top coat layer and a polyimide were spin-coated thereon to a thickness of about 500 angstroms to form an alignment film. S on the back
The chemical-resistant coating agent of the above (10) was similarly spin-coated and cured on the iOx vapor-deposited film to form a top coat layer.
Next, a liquid crystal material was injected between the two substrates, sealed with a sealing member, and a polarizing plate was further laminated on the outer surface to obtain a liquid crystal display device. No problem occurred in the manufacturing process. The image quality of the liquid crystal display device obtained in this manner was equivalent to that of a liquid crystal display device using a glass substrate. Table 3 shows the results.

Example 2 Raw materials having a viscosity average molecular weight of 16000 and LT85 to 90
%, Polycarbonate 1/1 (for structural formula, see Table 2) and a 1/1 mixture of P (melted and mixed by a twin-screw extruder; Tg of the mixture is 170 ° C), and the pressing temperature is set to 250 ° C
Production and evaluation were carried out in the same manner as in Example 1 except for the above.

Example 3 As a raw material, a 1/1 mixture of a polycarbonate Z '(n = 55) having a viscosity average molecular weight of 23000 shown in the structural formula of Table 2 and a polycarbonate A having a viscosity average molecular weight of 15000 (melt and mixed by a twin screw extruder). Performed: LT85
Example 1 except that (Tg 175 ° C.) was used.
Production and evaluation were performed in the same manner as described above.

Comparative Example 1 Raw materials having a viscosity average molecular weight of 16,000 and LT 85 to 90
% And a Tg of 145 ° C., and the production and evaluation were performed in the same manner as in Example 1 except that the thickness of the injection compression plate was 1 mm. However, the surface roughness of this substrate deteriorated due to insufficient heat resistance during the formation of the ITO sputtered film and the subsequent formation of the alignment film, and the assembled LCD substrate developed color bleeding.

Comparative Example 2 Raw materials having a viscosity average molecular weight of 20,000 and LT85 to 90
%, Using polycarbonate P having a Tg of 181 ° C., dissolving this resin in methylene chloride, casting the solvent on a steel plate, and removing the solvent by drying to obtain a 0.1 mm thick film. In the liquid crystal display element assembled by using this film, color bleeding occurred because the film lacked the self-supporting property.

Comparative Example 3 Raw materials having a viscosity average molecular weight of 17000 and LT85 to 90
%, A polycarbonate P having a Tg of 180 ° C. was used and evaluated in the same manner as in Example 1 except that a stainless steel plate having a surface roughness of Ra = 0.2 μm was used during hot press treatment. 5 inch diagonal STN assembled with this board
In the liquid crystal display device, color bleeding occurred because the surface roughness of the substrate was insufficient.

Comparative Example 4 A resin substrate was manufactured in the same manner as in Example 1 except that a cyclic polyolefin resin having a structure shown in Table 2 and having a Tg of 170 ° C. was used as a raw material. When the impact strength test of this substrate was performed, the minimum breaking energy value was 480 gf · cm.

Comparative Example 5 An optically polished glass flat plate was used as a spacer with a width of 5 m.
A cavity was formed using a silicon plate having a thickness of 0.8 mm and a thickness of 0.8 mm, and a peripheral portion was sealed with a tape to form an injection mold. 99 parts by weight of p-bis (β-methacryloyloxyethylthio) xylene, 1 part by weight of pentaerythritol tetrakis (β-thiopropionate) as a photocurable resin, 2,4,6-trimethylbenzoyldiphenylphosphine as a photoinitiator 0.06 parts by weight of oxide (“Lucillin TPO” manufactured by BASF), benzophenone 0.0
After uniformly stirring and mixing 4 parts by weight, the composition was defoamed to obtain a composition. This composition was injected into an injection mold, and cured by irradiating ultraviolet rays for 30 minutes between metal halide lamps having an output of 80 W / cm above and below at a distance of 400 mm from the glass surface. The injection mold was removed to obtain a resin substrate made of a photocurable resin. When the impact strength test of this substrate was performed, the minimum breaking energy value was 550 gf · cm.

Comparative Example 6 As a raw material, a viscosity average molecular weight was 35,000, and LT was 85 to 90.
% And a Tg of 184 ° C., and the production and evaluation were performed in the same manner as in Example 1 except that the thickness of the injection compression plate was 0.8 mm. Since the resin substrate had a large molecular weight and did not sufficiently relax the orientation during the hot press treatment and had a large birefringence value, color bleeding occurred on the screen after assembling into a 5-inch diagonal liquid crystal display element.

Comparative Example 7 Raw materials having a viscosity average molecular weight of 8000 and LT 85 to 90
%, A polycarbonate substrate having a Tg of 170 ° C. was used, and a resin substrate was obtained in the same manner as in Example 1 except that the thickness of the injection compression plate was set to 0.8 mm. However, since the substrate had insufficient molecular weight, a crack was formed in the substrate upon peeling from the stainless steel plate, and the minimum fracture energy value was 580 gf · cm when the impact resistance test of the peeled piece was performed. .

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

Example 4 Viscosity average molecular weight 14000, LT 85-90%, Tg =
Using 180 ° C polycarbonate P (see Table 2 for the structural formula), a 200-ton injection machine (M-200B) manufactured by Meiki Seisakusho
A flat plate having a thickness of 0.8 mm and a size of 5 × 5 cm was formed by injection compression molding.

Subsequently, the hot press was previously heated to 100 ° C., and before the obtained molded plate absorbed moisture, both surfaces thereof were sandwiched between stainless steel plates having a surface roughness Ra of 0.004 μm.
It heated to 15 degreeC over 15 minutes, and performed press heat treatment. The pressing temperature was 260 ° C., the time was 20 minutes, and the pressing pressure was 50 g / cm ² during the last 5 minutes at 260 ° C. The heat press treatment was performed in an oven, but the atmosphere pressure in the oven was 750 mmHg, and the oxygen concentration was 1% by volume.
Met. After hot pressing, the substrate was cooled to 130 ° C. over 20 minutes while sandwiching the substrate between stainless steel plates.
When the temperature reached ℃, when the stainless steel plate was peeled off with a screwdriver, the resin substrate was still stuck to one of the stainless steel plates. Was.

Further, the peeled substrate was kept in an oven at 145 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 5 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.004.
μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
This transparent resin substrate had no particular problem in visual appearance. Table 3 summarizes the heat treatment conditions of the substrates used in the examples and the comparative examples and the evaluation results of the processed substrates.

Example 5 Polycarbonate A having a viscosity average molecular weight of 16,000 (see Table 2 for the structural formula) as a raw material and a viscosity average molecular weight of 1200
0: 1/1 mixture of P (melt mixing was carried out by a twin screw extruder. Viscosity average molecular weight: 14000, LT85-9)
0%, Tg = 170 ° C.), and an A5 plate was molded in the same manner as in Example 4. The press machine was previously heated to 120 ° C., the molded plate was put therein, and heated to 250 ° C. over 6 minutes. The pressing temperature was 250 ° C., the time was 15 minutes, and the atmospheric pressure in the oven was 30 mmHg. The pressing pressure was 30 g / cm ² during the last 5 minutes at 250 ° C. Thereafter, the mixture was cooled from 250 ° C. to 130 ° C. over 5 minutes, and was separated and annealed in the same manner as in Example 4 to obtain a target resin substrate. The birefringence of this substrate is
Single pass retardation on the entire substrate 0-5n
m, and the surface roughness was Ra = 0.005 μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more. This transparent resin substrate had no particular problem in visual appearance.

Example 6 Polycarbonate Z 'represented by the structural formula of Table 2 having a viscosity average molecular weight of 23,000 as a raw material and a viscosity average molecular weight of 1500
0 mixture of polycarbonate A (melt mixing was carried out by a twin screw extruder. Viscosity average molecular weight 1800)
0, LT 85-90%, Tg = 175 ° C.), and an A5 plate was produced in the same manner as in Example 4. The press machine preheats to 140 ° C.
Heat to 30 ° C. over 30 minutes. Press temperature is 260 ℃,
The time was 8 minutes, and the atmospheric pressure in the oven was 30 mmHg. The pressing pressure was 40 g / cm ² at 260 ° C. Thereafter, the mixture was cooled from 260 ° C. to 140 ° C. over 4 minutes, and separated at 140 ° C. in the same procedure as in Example 4.
Annealing was performed at 50 ° C. to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 5 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is R
a = 0.008 μ was obtained. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more. Regarding this transparent resin substrate,
There was no particular problem.

Example 7 1/100 of polycarbonate Z 'having a viscosity average molecular weight of 23,000 and polycarbonate A having a viscosity average molecular weight of 15,000
1 mixture (melt mixing was performed by a twin screw extruder. Viscosity average molecular weight 18000, LT 85 to 90%, Tg = 17
5 ° C) using a 200-ton injection machine manufactured by Meiki Seisakusho (M-
200B), a flat plate having a thickness of 3 mm and a size of 5 × 5 cm was formed by injection compression molding.

Subsequently, before this molded plate absorbs moisture, the surface roughness of the part forming a flat surface on both sides is Ra = 0.006.
Pressing heat treatment was performed by sandwiching a linear pattern having a thickness of 100 μm, a pitch of 100 μ, and a convex portion of 1 μ between engraved metal plates, and making the linear pattern perpendicular to the lattice on the front and back. The press machine was previously heated to 150 ° C., and the formed plate was put therein and heated to 260 ° C. over 30 minutes. Press temperature is 2
The temperature was 60 ° C., the time was 20 minutes, and the pressure during pressing was 50 g / cm ² for the last 10 minutes at 260 ° C. The hot press treatment was performed in an oven, and the atmospheric pressure in the oven was 20 mmHg.

After hot pressing, the substrate was cooled to 90 ° C. over 20 minutes while sandwiching the substrate between stainless steel plates.
When the stainless steel plate was spread out with a screwdriver, the resin substrate remained stuck to one of the stainless steel plates, but this can be easily removed by slowly rolling up the edge of the resin substrate. done.
Further, the peeled substrate was kept in an oven at 160 ° C. for about 2 hours and annealed to sufficiently reduce the residual stress to obtain a target transparent sheet. However, a slight yellow coloring was observed.

The birefringence of the present substrate was in the range of 0 to 5 nm over the entire surface of the substrate by a single-pass retardation, and the surface roughness of the portion constituting the plane was Ra = 0.007 μm. In addition, in the cross-sectional photograph by an atomic force microscope, it was confirmed that 90% or more of the cross-sectional area ratio was transferred to the resin substrate side with respect to the linear pattern of the metal plate. Further, in the impact strength test by the DuPont method, the impact strength was 100
It was not less than 00 gf · cm. This transparent resin substrate had no problems such as scratches and dents in visual appearance.

Comparative Example 8 Raw materials having a viscosity average molecular weight of 16000 and LT85 to 90
%, Tg = 148 ° C. using polycarbonate A,
An injection compression plate was prepared in the same manner as in Example 4 except that the thickness was A5 and the thickness was mm. Subsequently, before the molded plate absorbed moisture, press heat treatment was performed by sandwiching both surfaces of the molded plate between stainless steel plates having a surface roughness Ra of 0.005 μm. The press machine preheats to 80 ° C, puts the formed plate into it,
And heated for 2 minutes. The pressing temperature was 140 ° C., the time was 20 minutes, and the pressure during pressing was 200 g / cm ² during the last 5 minutes at 140 ° C. The heat press treatment was performed in an oven, but the pressure in the oven was 20 mmHg.
Met. After hot pressing, the substrate was cooled to 100 ° C. in about 5 minutes while sandwiching the substrate between stainless steel plates.
When the temperature reached ℃, when the stainless steel plate was peeled off with a screwdriver, the resin substrate remained attached to one of the stainless steel plates, but this could be easily peeled off by slowly rolling up the end of the resin substrate. .

Further, the peeled substrate was kept in an oven at 120 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of the present substrate was in the range of 15 to 25 nm over the entire surface of the substrate by single-pass retardation due to insufficient hot press temperature, and the surface roughness was Ra = 0.02 μm. In the impact strength test by the DuPont method, the impact strength was 100
Although it was not less than 00 gf · cm, irregularities were visually observed.

Comparative Example 9 As raw materials, viscosity average molecular weight 20,000, LT85-90
%, Using polycarbonate P having a Tg of 182 ° C. and a 0.8-ton injection machine (M-200B) manufactured by Meiki Seisakusho.
A flat plate having a thickness of 5 mm and a size of 5 × 5 cm was formed by injection compression molding. Subsequently, before the molded plate absorbed moisture, press heat treatment was performed by sandwiching both surfaces of the molded plate between stainless steel plates having a surface roughness Ra of 0.005 μm. Press machine is 16
Heat to 0 ° C, put the formed plate there
Heated for 0 minutes. Press temperature 320 ° C, time 3
At 0 minutes, the pressure during pressing was 10 g / cm ² during the last 3 minutes at 320 ° C. The hot pressing was performed in an oven, and the pressure in the oven was 30 mmHg. After the hot press treatment, the substrate was cooled to 140 ° C over 20 minutes with the substrate sandwiched between the stainless steel plates. When the entire temperature reached 140 ° C, the stainless steel plate was peeled off with a screwdriver. However, peeling was performed by slowly rolling up the end of the resin substrate. However, some cracks were formed during peeling.
This is considered to be due to embrittlement and poor peeling due to thermal degradation of the resin.

Further, the peeled substrate was held in an oven at 145 ° C. for about 2 hours to carry out annealing, thereby sufficiently relaxing the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 5 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.004.
μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
However, the transparent resin substrate was visually colored yellow in appearance.

Comparative Example 10 Raw materials having a viscosity average molecular weight of 14000 and LT85 to 90
%, Tg = 180 ° C. using polycarbonate P,
An injection compression plate was manufactured in the same manner as in Example 4 except that the thickness was A5 mm. Subsequently, before this molded plate absorbed moisture, press heat treatment was performed by sandwiching both surfaces between stainless steel plates having a surface roughness Ra of 0.02 μm. The press machine preheats to 100 ° C, puts the formed plate into it,
Until 10 minutes. The pressing temperature was 240 ° C., the time was 20 minutes, and the pressing pressure was 50 g / cm ² during the last 10 minutes at 240 ° C. The heat press treatment was performed in an oven, but the pressure in the oven was 50 mmH.
g. After hot pressing, the substrate was cooled to 140 ° C. over 20 minutes with the substrate sandwiched between stainless steel plates.
When the temperature reached 0 ° C, the stainless steel plate was peeled off with a screwdriver. The resin substrate remained attached to one of the stainless steel plates. Was.

Further, the peeled substrate was kept in an oven at 140 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 5 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.07 μm.
m. In addition, in the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more, but a point where the surface was not mirror-finished was visually observed. After that, color bleeding occurred on the screen.

Comparative Example 11 Raw materials having a viscosity average molecular weight of 16,000 and LT85 to 90
%, Tg = 180 ° C. using polycarbonate P,
An injection compression molded plate was produced in the same manner as in Example 4 except that the plate was 0.7 mm thick and A5 size. Subsequently, the press machine was previously heated to 100 ° C., and before the obtained molded plate absorbed moisture, both surfaces thereof were sandwiched between stainless steel plates having a surface roughness Ra of 0.004 μm, and heated to 240 ° C. for 10 minutes, Press heat treatment was performed. The pressing temperature is 240 ° C, the time is 20 minutes, and the pressing pressure is 40 ° C in the last 15 minutes at 240 ° C.
g / cm ² . The hot press treatment was performed in an oven. The pressure in the oven was 760 mmHg, and the oxygen concentration was 1% by volume. After hot pressing, the substrate was cooled to 140 ° C over about 20 minutes with the substrate sandwiched between the stainless plates. When the entire temperature reached 140 ° C, the stainless plate was peeled off with a screwdriver. Although it was left as it was, it could be removed by slowly rolling up the edge of the resin substrate.

Further, the peeled substrate was held in an oven at 140 ° C. for about 2 hours to carry out annealing, thereby sufficiently reducing the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 5 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.006.
μm. Further, in the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more, but yellowing was observed in the peripheral portion by visual observation, and the atmosphere pressure was high while the area was large in A5 size. As a result, degassing was insufficient, and the incorporation of air bubbles was observed.

Comparative Example 12 Raw materials having a viscosity average molecular weight of 18,000 and LT85 to 90
%, Tg = 181 ° C. using polycarbonate P,
An injection compression plate was manufactured in the same manner as in Example 4, except that the plate was 0.6 mm thick and A5 size. Then, press the press machine beforehand.
The sheet was heated to 0 ° C. and before the obtained molded sheet absorbed moisture, both surfaces thereof were sandwiched between stainless steel sheets having a surface roughness Ra of 0.004 μm, and heated to 240 ° C. for 10 minutes to perform press heat treatment. The pressing temperature was 240 ° C., the time was 20 minutes, and the pressing pressure was 40 g /
cm ² . The hot pressing was performed in an oven, and the pressure in the oven was 120 mmHg. After hot pressing, the substrate was cooled to 120 ° C over about 20 minutes with the substrate sandwiched between the stainless plates. When the entire temperature reached 120 ° C, the stainless plate was peeled off with a screwdriver. Adhering
Furthermore, it was broken and could not be peeled off cleanly.

Comparative Example 13 Raw materials having a viscosity average molecular weight of 18000 and LT85 to 90
%, Tg = 181 ° C. using polycarbonate P,
An injection compression plate was manufactured in the same manner as in Example 4, except that the plate was 0.6 mm thick and A5 size. Then, press the press machine beforehand.
The sheet was heated to 0 ° C. and before the obtained molded sheet absorbed moisture, both surfaces thereof were sandwiched between stainless steel sheets having a surface roughness Ra of 0.004 μm, and heated to 240 ° C. for 10 minutes to perform press heat treatment. The pressing temperature was 240 ° C., the time was 20 minutes, and the pressing pressure was 40 g /
cm ² . The hot pressing was performed in an oven, and the pressure in the oven was 60 mmHg. After hot pressing, the substrate was cooled to 70 ° C over about 20 minutes with the substrate sandwiched between stainless steel plates. When the whole reached 70 ° C, the stainless steel plate was peeled off with a screwdriver, and the resin substrate was broken and fragmented. Was.

Comparative Example 14 Polycarbonate Z ′ (L having a viscosity average molecular weight of 30,000)
T90%, Tg = 208 ° C.)
3 to 5 mm using a 00 ton injection machine (M-200B)
A flat plate having a size of 5 cm was molded by injection compression molding.
Subsequently, the press machine was previously heated to 180 ° C., and before the obtained molded plate absorbed moisture, the surface roughness of the surface constituting both surfaces was Ra = 0.006 μm, and the pitch was 100 mm.
The sheet was sandwiched between metal plates engraved with a linear pattern of μ and a convex portion of 1μ, heated to 230 ° C. for 10 minutes, and subjected to a press heat treatment so that the linear pattern was perpendicular to the lattice on the front and back. The pressing temperature is 230 ° C., the time is 20 minutes, and the pressing pressure is 50 g / cm ^{2 for} the last 10 minutes at 230 ° C.
Met.

The hot pressing was performed in an oven.
The atmosphere pressure in the oven was 20 mmHg. After hot pressing, the substrate was cooled to 60 ° C over 20 minutes with the substrate sandwiched between the stainless steel plates. When the entire temperature reached 60 ° C, the stainless steel plate was pushed and spread by a screwdriver. Was in. Peel off the cracked resin substrate by rolling up the end,
Further, the peeled substrate was kept in an oven at 160 ° C. for about 2 hours to carry out annealing to reduce residual stress and obtain a transparent sheet.

The birefringence of the present substrate reached a maximum of 30 nm over the entire surface of the substrate by single-pass retardation, and was 20 nm on average. The surface roughness of the part constituting the plane was Ra = 0.01 to 0.02 μm. Further, in the cross-sectional photographing with an atomic force microscope, only 60% or less of the cross-sectional area ratio with respect to the linear pattern of the metal plate was transferred to the resin substrate side.

[0097]

[Table 4]

[0098]

[Table 5]

Example 8 Polycarbonate (1,1-bis (4-hydroxyphenyl)-having a viscosity average molecular weight of 18,000 and a Tg of 178 ° C.
The 3,3,5-trimethylcyclohexane unit (see Table 2 for the structural formula) and the bisphenol A unit are 55 /
Using a 55/45 melt mixture of A-polycarbonate (see Table 2 for the structural formula) containing the copolymer contained in No. 45 and a 0.2-ton injection machine (M-200B) manufactured by Meiki Seisakusho, Ltd.
A flat plate having a thickness of 8 mm and a size of 5 × 5 cm was formed by injection compression molding.

Subsequently, the press machine was heated to 100 ° C. in advance, and both sides of the obtained molded plate were subjected to surface accuracy Ra = 0.00 while taking care not to contaminate the surface before absorbing moisture.
It was sandwiched between 4 μm stainless steel plates, heated to 260 ° C. over 10 minutes, and subjected to press heat treatment. Press temperature is 260
C., the time was 20 minutes, and the pressing pressure was 50 g / cm ² in the last 5 minutes at 260 ° C.
The heat press treatment was performed in an oven, but the atmosphere pressure in the oven was 750 mmHg, and the oxygen concentration was 0.1% by volume.
It was below. After hot pressing, the substrate was cooled to 100 ° C. over 20 minutes while sandwiching the substrate between stainless steel plates.
When the temperature reached 00 ° C, the stainless steel plate was peeled off with a screwdriver, and the resin substrate was still stuck to one of the stainless steel plates. done. The thickness of this substrate was 0.5 mm.

Further, the peeled substrate was kept in an oven at 150 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 2 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.004.
μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
This transparent resin substrate had no particular problem in visual appearance. Also, using this substrate, a 5 inch diagonal STN
When the liquid crystal display panel was assembled, no inconvenience such as color blur was observed.

Example 9 Polycarbonate (1,1-bis (4-hydroxyphenyl)-having a viscosity average molecular weight of 19000 and a Tg of 208 ° C.
Copolymer containing 3,3,5-trimethylcyclohexane unit and bisphenol A unit at 55/45)
Using a 200-ton injection machine manufactured by Meiki Seisakusho (M-200
Using B), a flat plate having a thickness of 0.8 mm and a size of 5 × 5 cm was formed by injection compression molding.

Subsequently, the press machine was previously heated to 100 ° C., and both surfaces of the obtained molded plate were subjected to surface accuracy Ra = 0.00 while taking care not to contaminate the surface before absorbing moisture.
It was sandwiched between stainless steel plates of 4 μm and heated to 280 ° C. for 10 minutes to perform press heat treatment. Press temperature is 280
C., the time was 10 minutes, and the pressure at the time of pressing was 10 g / cm ² in the last 3 minutes when 280 ° C. was applied.
The hot press treatment was performed in an oven, and the atmospheric pressure in the oven was 10 mmHg or less. After the heat press treatment, the substrate was sandwiched between stainless steel plates for 12 minutes over 20 minutes.
When cooled down to 0 ° C and the whole temperature reached 120 ° C, the stainless steel plate was peeled off with a screwdriver. The resin substrate remained stuck to one of the stainless steel plates. It was easy to remove by raising. The thickness of this board is 0.6mm
Met.

Further, the peeled substrate was held in an oven at 180 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 5 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.005.
μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
This transparent resin substrate had no particular problem in visual appearance. Also, using this substrate, a 5 inch diagonal STN
When the liquid crystal display panel was assembled, no inconvenience such as color blur was observed.

Comparative Example 15 Raw materials having a viscosity average molecular weight of 14,000 and Tg = 180 ° C.
Using polycarbonate P (see Table 2 for the structural formula)
An injection compression plate was produced in the same manner as in Example 8 except that the A5 plate was 1 mm thick. Subsequently, the press machine was previously heated to 100 ° C.
Before the obtained molded plate absorbs moisture, sandwiching both surfaces thereof with a stainless steel plate having a surface roughness Ra = 0.005 μm,
It heated to 200 degreeC over 10 minutes, and performed press heat treatment. The pressing temperature is 200 ° C., the time is 30 minutes, and the pressing pressure is 250 g / cm in the last 5 minutes at 200 ° C.
^{Was 2} . The heat press treatment was performed in an oven,
The pressure in the oven was 20 mmHg. After hot pressing, the substrate was sandwiched between stainless steel plates and cooled to 100 ° C over about 20 minutes. When the entire temperature reached 100 ° C, the stainless steel plate was peeled off with a screwdriver. Although it was left as it was, it could be easily peeled off by slowly rolling up the edge of the resin substrate.

Further, the peeled substrate was held in an oven at 150 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 5 to 25 nm over the entire surface of the substrate with single-pass retardation due to lack of hot press temperature and stacking of benzene rings due to the structure containing an aromatic ring in the methylene portion of bisphenol, Due to insufficient hot press temperature, the surface roughness was Ra = 0.15 μm.
In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
Irregularities were observed. When a 5 inch diagonal STN liquid crystal display panel was assembled using this substrate, a clear screen could not be obtained due to color bleeding.

Comparative Example 16 Polycarbonate (1,1-bis (4-hydroxyphenyl)-having a viscosity average molecular weight of 18,000 and a Tg of 178 ° C.
A copolymer containing a 3,3,5-trimethylcyclohexane unit and a bisphenol A unit in a ratio of 55/45;
(55-45 melt mixture with A-polycarbonate) and dissolved in methylene chloride, and the solution was cast on a mirror-finished stainless steel plate. After the solvent was sufficiently evaporated and dried, the film was peeled off from the stainless steel plate to obtain a film having a thickness of 150 μm.

Subsequently, the press machine was previously heated to 100 ° C., and before the obtained molded plate absorbed moisture, both surfaces thereof were sandwiched between stainless steel plates having a surface accuracy of Ra = 0.005 μm and heated to 260 ° C. for 20 minutes. Then, press heat treatment was performed. The pressing temperature is 260 ° C, the time is 20 minutes, and the pressing pressure is 26
1000 g / cm ² during the last minute at 0 ° C. The hot pressing was performed in a vacuum oven, and the pressure in the oven was 30 mmHg. After hot pressing, the substrate was sandwiched between stainless steel plates for 10 minutes,
After cooling to 0 ° C., when the whole reached 110 ° C., the stainless steel plate was peeled off with a screwdriver, but the resin substrate was still attached to one of the stainless steel plates, but by slowly rolling up the end of the resin substrate, By peeling, a film having a thickness of 90 μ was obtained.

Further, the peeled substrate was kept in an oven at 150 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of this substrate is in the range of 0 to 3 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.004.
μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
However, regarding this transparent resin substrate, when a diagonal 5-inch STN liquid crystal display panel is assembled using this substrate, the thickness is thin. Since the gap between the substrates could not be kept constant, color bleeding occurred and a clear image could not be obtained.

Comparative Example 17 Raw materials having a viscosity average molecular weight of 14,000 and Tg = 180 ° C.
An injection compression plate was manufactured in the same manner as in Example 8 except that the polycarbonate P was used and a 1 mm thick A5 plate was used.
Subsequently, the press machine was previously heated to 100 ° C., and both surfaces of the obtained molded plate were subjected to surface accuracy Ra = 0.05 before the molded plate absorbed moisture.
It was sandwiched between 2 μm stainless steel plates, heated to 240 ° C. over 10 minutes, and subjected to press heat treatment. Press temperature is 240
C., the time was 20 minutes, and the pressing pressure was 1050 g / cm ² in the last 3 minutes at 240 ° C. The hot pressing was performed in an oven, but the pressure in the oven was 5
It was 0 mmHg. After hot pressing, the substrate was cooled to 120 ° C over 20 minutes with the substrate sandwiched between the stainless steel plates. When the entire temperature reached 120 ° C, the stainless steel plate was peeled off with a screwdriver. However, this could be easily removed by slowly rolling up the edge of the resin substrate.

Further, the peeled substrate was held in an oven at 150 ° C. for about 2 hours to carry out annealing, thereby sufficiently relaxing the residual stress to obtain a target resin substrate. The birefringence of the present substrate is in the range of 5 to 30 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.07.
μm. In the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more.
When a 5 inch diagonal STN liquid crystal display panel was assembled using this substrate, the benzene ring stacking caused by the structure containing an aromatic ring in the methylene portion of bisphenol and the pressure during hot pressing were excessively high, resulting in birefringence. Was not sufficiently reduced, color bleeding occurred, and a clear screen could not be obtained.

Comparative Example 18 Raw materials having a viscosity average molecular weight of 16,000 and Tg = 150 ° C.
An injection compression plate was manufactured in the same manner as in Example 8 except that the polycarbonate A was used and a 0.7 mm thick A5 plate was used. Subsequently, the press machine was heated to 100 ° C. in advance, and both sides of the obtained molded plate were subjected to surface accuracy Ra = 0.004 μm while taking care not to contaminate the surface before absorbing moisture.
m, and heated to 240 ° C. for 10 minutes to perform a press heat treatment. Press temperature is 240 ° C,
The time was 20 minutes and the pressure during the press was 40 g / cm ² during the last 5 minutes at 240 ° C. The heat press treatment was performed in an oven, but the pressure in the oven was 760 mmH.
g and oxygen concentration were 18% by volume. After hot pressing
With the substrate sandwiched between stainless steel plates, it takes 110
The stainless steel plate was peeled off with a screwdriver when the temperature reached 110 ° C. A substrate sample was obtained.

Further, the peeled substrate was held in an oven at 120 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. The birefringence of the present substrate is in the range of 2 to 25 nm over the entire surface of the substrate by single-pass retardation, and the surface roughness is Ra = 0.00.
It was 6 μm. Further, in the impact strength test by the DuPont method, the impact strength was 10,000 gf · cm or more, but yellowing was observed in the peripheral portion by visual observation, and the atmosphere pressure was high while the area was large in A5 size. As a result, degassing was insufficient, and the incorporation of air bubbles was observed.

Comparative Example 19 Raw materials having a viscosity average molecular weight of 30,000 and Tg = 210 ° C.
(A copolymer containing a 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane unit and a bisphenol A unit at a ratio of 55/45), and a sheet having a thickness of 1.0 mm was used. It was formed by an extrusion method using a polishing roll.

Subsequently, the press machine was heated to 180 ° C. in advance, and both sides of the obtained molded plate were subjected to surface accuracy Ra = 0.00 while taking care not to contaminate the surface before absorbing moisture.
It was sandwiched between stainless steel plates of 4 μm and heated to 280 ° C. for 10 minutes to perform press heat treatment. Press temperature is 280
C., the time was 10 minutes, and the pressing pressure was 50 g / cm ² in the last 5 minutes at 280 ° C. The heat press treatment was performed in an oven, but the pressure in the oven was 20 m.
mHg. After hot pressing, the substrate was sandwiched between stainless steel plates and cooled to 120 ° C over about 20 minutes. When the entire temperature reached 120 ° C, the stainless steel plate was peeled off with a screwdriver. Although it was left as it was, it could be easily peeled off by slowly rolling up the edge of the resin substrate.

Further, the peeled substrate was kept in an oven at 180 ° C. for about 2 hours to carry out annealing to sufficiently reduce the residual stress to obtain a target resin substrate. This board is
Due to the large molecular weight, excessive shrinkage stress is generated at the same time as the orientation is relaxed during heating, and sufficient low birefringence and surface properties cannot be obtained.
The surface roughness is Ra ≧ 0.1 μm in the range of 5 to 35 nm.
m, and a clear undulation was visually observed. In the impact strength test by the DuPont method, the impact strength was 1000
0 gf · cm or more.

Comparative Example 20 Raw materials having a viscosity average molecular weight of 18,000 and Tg = 178 ° C.
55/45 melt mixture of A-polycarbonate with a copolymer containing 55/45 of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane unit and bisphenol A unit ), And an injection compression plate was produced in the same manner as in Example 8 except that the plate was 0.6 mm thick and A5 size.

Subsequently, the press was previously heated to 120 ° C., and before the obtained molded plate absorbed moisture, both surfaces thereof were sandwiched between stainless plates having a surface accuracy of Ra = 0.004 μm.
Until 10 minutes, and press heat treatment was performed. The pressing temperature is 260 ° C, the time is 10 minutes, and the pressing pressure is 2
50 g / cm ² during the last 5 minutes at 60 ° C. The hot pressing was performed in an oven, and the pressure in the oven was 60 mmHg. After hot pressing, the substrate was cooled to 60 ° C over about 20 minutes with the substrate sandwiched between the stainless steel plates. When the whole reached 60 ° C, the stainless steel plate was peeled off with a screwdriver, and the resin substrate was broken and fragmented. Was.

[0119]

The transparent resin optical sheet and optical component of the present invention have excellent moldability, lightness, toughness, and optical isotropy.
It is very useful as various optical components such as display device components such as liquid crystal displays, and its industrial utility value is extremely large.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G02B 5/00 G02B 5/00 Z 4J029 G02F 1/1333 500 G02F 1/1333 500 5C094 G09F 9/30 310 G09F 9/30 310 // C08G 63/64 C08G 63/64 C08J 5/18 CFD C08J 5/18 CFD (31) Claimed priority number Japanese Patent Application No. 10-256430 (32) Priority date September 10, 1998 (September 1998) .10) (33) Countries claiming priority Japan (JP) F-term (reference) 2H042 AA07 AA18 AA20 AA21 AA26 AA30 AA33 2H090 JB03 JB07 JC08 JD13 KA08 LA05 4F071 AA50 AA81 AA86 AF23Y AF27Y AF30A AF01A41 BB01 AK45A AK45J AL01A BA01 DD07 EJ20 EJ42 EJ59 EJ60 GB41 JA05A JB16A JK10 JN01 JN01A JN18 4J002 CG011 CG012 CG021 CG031 CG041 GP00 4J029 AA08 AA09 AB01 AC01 AD01 A03 HC03 DBA13A04 CA24 EA05 EB02 FB01 FB15 GB10 JA08 JA13 JA20

Claims (19)

[Claims] 1. A resin sheet having a thickness of 0.2 to 1.5 mm made of a transparent resin having a light transmittance of 80% or more by visible light and a glass transition temperature of 150 ° C. or more, and having a birefringence of 15 nm. Hereinafter, the surface roughness Ra is 0.1 μm
An optical sheet made of a transparent resin, having an impact strength of not more than 600 gf · cm as measured by a DuPont drop ball impact test. 2. The method according to claim 1, wherein the transparent resin is a thermoplastic resin.
4. The optical sheet made of a transparent resin according to item 1. 3. The optical sheet according to claim 2, wherein the transparent resin is polycarbonate or polyester carbonate. 4. The transparent resin has a viscosity average molecular weight of 10,000.
The transparent resin optical sheet according to any one of claims 1 to 3, wherein 5. The transparent resin has a glass transition temperature of 130 ° C.
The transparent resin optical sheet according to any one of claims 1 to 4, wherein the transparent resin optical sheet contains at least 5 mol% of the carbonate binding unit having a cyclic aliphatic group based on all the carbonate binding units. 6. The transparent resin optical sheet according to claim 5, wherein the cyclic aliphatic group contained in the carbonate binding unit is introduced from 1,1-bis (4-hydroxyphenyl) cyclohexane. 7. The resin sheet has a thickness of 0.4 to 1.1 m.
The transparent resin optical sheet according to any one of claims 1 to 6, which is m. 8. An impact strength of 100 at break energy value.
The transparent resin optical sheet according to any one of claims 1 to 7, which is at least 00 gf · cm. 9. A transparent resin in which a polycarbonate resin containing a polycarbonate binding unit having a cyclic aliphatic group and a carbonate resin having a bisphenol A unit are mixed at a weight ratio of 2: 8 to 8: 2. An optical sheet made of a transparent resin according to any one of claims 1 to 8. 10. The transparent resin optical sheet according to claim 1, wherein the transparent resin optical sheet is used for a liquid crystal display element. 11. The communication system according to claim 1, wherein the application is for communication.
The optical sheet for transparent resin according to any one of the above. 12. An optical part made of a transparent resin having a visible light transmittance of 80% or more and a glass transition temperature of 80 ° C. or more, a birefringence of 15 nm or less, and a surface roughness Ra of 0. An optical component made of a transparent resin, having a size of 1 μm or less. 13. The transparent resin optical component according to claim 12, wherein the birefringence is 15 nm or less, and the thickness of the thickest portion is 0.2 mm or more. 14. A transparent resin having a light transmittance of 80% or more by visible light and a glass transition temperature of 80 ° C. or more, or a transparent resin processed product thereof is hot-pressed at a temperature represented by the following formula (1). A method for producing the transparent resin optical sheet according to claim 1. (Equation 1) 15. A surface sandwiching the transparent resin or the transparent resin processed body from above and below at the time of the hot press treatment is made of a metal material or an inorganic material, and the surface roughness Ra of the portion constituting the plane is reduced. 2. The method according to claim 1, wherein the thickness is 0.1 μm or less.
5. The method for producing a transparent resin optical sheet according to item 4. 16. The method for producing a transparent resin optical sheet according to claim 14, wherein the transparent resin processed body is manufactured by injection molding. 17. The method for producing a transparent resin optical sheet according to claim 14, wherein the periphery of the transparent resin or the transparent resin processed body is an inert gas atmosphere or a vacuum during the hot press treatment. . 18. The time average of the press pressure in the hot press treatment at least in the last one minute or more under the temperature range of the above formula (1) is 0 to 1000 (g / c).
The method for producing a transparent resin optical sheet according to any one of m ²⁾ is in the range of claims 14 to 17. 19. The temperature D (° C.) at which the transparent resin or the transparent resin processed body is peeled off from the surface sandwiching the transparent resin after the hot press treatment is within the range of the following expression, and Tg> D ≧ Tg− 120 (where Tg represents the glass transition temperature (° C.) of the resin). After peeling from the hot press state, the peeled molded body is annealed at a temperature represented by the following formula. A method for producing a transparent resin optical sheet according to any one of the above. ## EQU3 ## Tg-10> D ≧ Tg-50