JP3092326B2 - Lid for CCD - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a CCD [charge]
And a lid [LID (cover)] for a coupled device.

[0002]

2. Description of the Related Art CCD sensors are facsimile, AF
There are two types, a linear (one-dimensional) CCD used for cameras and bar code readers, and an area (two-dimensional) CCD used for video cameras and industrial cameras. General C
The structure of the CD sensor is a hollow structure in which a CCD chip is embedded in ceramics and covered with a glass lid. The glass lid is bonded to ceramics to protect the CCD chip from dust, moisture, and the like. Since it is necessary to read information through the lid, the lid must have high transparency to allow visible light to pass therethrough, low absorption to protect the CCD chip from moisture and the like, and low water permeability. In addition, the birefringence of the lid must be small in order to prevent image distortion. In addition, the lid is bonded to the ceramic by holding it at a high temperature, usually using an epoxy adhesive. In addition, devices using a CCD, such as an AF camera and a video camera, are often left in a car, and must not be deformed at high temperatures. Therefore, the lid material is also required to have heat resistance.

[0003] From the above characteristics, glass is used as a lid material, and a thin glass lid made of glass has been put to practical use. This glass lid usually has a thickness of 1 mm
Alternatively, a thin film having a surface flatness excellent on both surfaces is used. However, this glass lid is extremely thin and often breaks during manufacturing. Moreover, the glass lid may be polished and finished to provide smoothness in addition to thinness.
This operation cracks and the yield is further reduced. Further, the glass lid of the thin film is often broken during the work of attaching it to the CCD, and the use of the glass lid causes a problem in workability in assembling. Furthermore, devices using CCDs are suitable for weight reduction and miniaturization, and have problems in strength and workability, such as the fact that glass cannot be made thinner in addition to having a higher specific gravity.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is characterized by excellent properties of glass such as heat resistance, transparency, low birefringence, and low water absorption. A CCD lid that maintains all the necessary physical properties at a practical level, improves the workability and workability resulting from the fragility of glass, and enables the use of CCDs to be reduced in size and weight. The purpose is to provide.

[0005]

SUMMARY OF THE INVENTION The present invention provides a light transmittance (hereinafter, sometimes referred to as "light transmittance") having a heat deformation temperature of 70 ° C. or more and a wavelength of 400 nm to 900 nm.
Is 80% or more, and the absolute value of the photoelastic coefficient is 10 ⁻¹⁰ cm ² /
dyne or less, and the saturated water absorption is 2% by weight or less .
And norbornene represented by the following general formulas (I) to (IV)
An object of the present invention is to provide a CCD lid made of an organic polymer material having at least one skeleton .

[0006]

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[0007]Wherein A, B, C and D are hydrogen
, A hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a halo
A C 1-10 hydrocarbon group substituted with a gen atom,-
(CH _Two ) _n COOR ¹ ,-(CH _Two ) _n OCOR ¹ ,
− (CH _Two ) _n OR ¹ ,-(CH _Two ) _n CN,-(CH
_Two ) _n CONR ^Three R ^Two ,-(CH _Two ) _n COOOZ,-
(C H _Two ) _n OCOZ,-(CH _Two ) _n OZ,-(CH
_Two ) _n Consists of W, or B and C  Or a (poly) cyclic alkylene group. here,
R ¹ , R ^Two , R ^Three And R ^Four Is a carbonized carbon having 1 to 20 carbon atoms.
A hydrogen group, Z is a hydrocarbon group substituted with a halogen atom, W
Is SiR ^Five _p F _3-p (R ^Five Is a hydrocarbon having 1 to 10 carbon atoms
Group, F is a halogen atom, -OCOR ⁶ Or -OR
⁶ (R ⁶ Represents a hydrocarbon group having 1 to 10 carbon atoms), and p represents
N represents an integer of 0 to 10). ]

[0008] The CCD lid of the present invention is composed of the above- mentioned organic polymer material, but must satisfy all the above-mentioned physical properties. That is, first, the organic polymer material used for the CCD lid of the present invention must have heat resistance. The higher the heat resistance, the more preferable from the viewpoint of the operating temperature of the device using the lid and the work of attaching the lid to the ceramic at a high temperature.
It is necessary to use a material having a heat deformation temperature specified in 648 of 70 ° C. or higher. From the viewpoint of use in a car and high-speed adhesion treatment to ceramics, the heat distortion temperature is 10
The temperature is 0 ° C or higher, more preferably 120 ° C or higher.

Further, the light transmittance needs to be 80% or more. The higher the light transmittance, the brighter the image becomes, so that it is preferably 85% or more, and more preferably 89% or more, which is the same level as that of glass. It is also possible to increase the light transmittance by attaching a well-known antireflection film used as a usual method to the lid.

Further, since the information displayed on the CCD is read through the lid, the distortion of the lid is an obstacle to reading the information accurately. Therefore, a lid with as little distortion as possible is required. The distortion of the compact is
It arises from the photoelastic coefficient, which is the physical property value of the material itself, and the residual strain during molding. The residual distortion can be adjusted by a molding method and molding conditions, and it is necessary to select a method and conditions that do not cause residual distortion according to the material, and molding can be performed using a known method.
However, the photoelastic coefficient, which is the intrinsic physical property of the material itself, cannot be changed, and its absolute value is 10
It is necessary to be less than ⁻¹⁰ cm ² / dyne. Small enough Preferably if the absolute value is smaller, 10 ^-11 c
m ² / dyne is more preferred.

Further, the saturated water absorption must be not more than 2% by weight from the viewpoints of protection of the CCD chip from humidity, fogging of the lid and adhesion of water droplets. This value is also
The smaller, the better, the better, 1% by weight or less, more preferably 0.5% by weight or less. Further, in order to reduce the water absorption, both sides or one surface of the lid can be coated with a material having high water absorption to enhance the water absorption.
Examples of the coating method include coating an inorganic material, for example, an oxide such as silicon, aluminum, tantalum, or niobium by a technique such as sputtering or vapor deposition. It is also possible to use a polymer material having low water absorption, for example, a polyolefin.

An organic polymer material which satisfies all the above-mentioned physical properties includes a compound represented by the general formula (I)
And a thermoplastic resin having a norbornene skeleton represented by (IV).

These thermoplastic resins having a norbornene skeleton are excellent in heat resistance and have a small photoelastic coefficient, so that birefringence is small, distortion is hardly generated, and an excellent lid for CCD can be provided. Further, from the viewpoint of the strength and moldability of the obtained CCD lid, the number average molecular weight of the thermoplastic resin used in the present invention is from 3,000 to 100.
10,000, preferably 8,000 to 200,000. In addition, these thermoplastic resins having a norbornene skeleton include various additives such as an antioxidant, a weathering agent, a release agent, a plasticizer, a plasticizer, in view of moldability, mold release properties, aesthetics, and durability. Abrasives,
A lubricant and the like can be added as needed.

Examples of the thermoplastic resin having a norbornene skeleton which can be used in the present invention include, for example, JP-A-60-168708 and JP-A-62-2524.
No. 06, JP-A-62-252407, JP-A-2-133413, JP-A-63-145324, JP-A-63-264626, JP-A-1-2
No. 40517, Japanese Patent Publication No. 57-8815, and the like. Specific examples of the thermoplastic resin include metathesis polymerization of at least one tetracyclododecene derivative represented by the following general formula (V) or an unsaturated cyclic compound copolymerizable with the tetracyclododecene. A hydrogenated polymer obtained by hydrogenating the obtained polymer can be exemplified.

[0015]

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(Wherein, A to D are the same as described above.) In the tetracyclododecene derivative represented by the general formula (V), A, B, C and D may each contain a polar group. This is preferable because it improves the adhesion to ceramics and facilitates various surface treatments. Furthermore, this polar group is-
The group represented by (CH ₂ ) _n COOR ¹ is preferable in that the obtained hydrogenated polymer has a high glass transition temperature.

In particular, one polar substituent consisting of the carboxylic acid ester group is contained per molecule of the tetracyclododecene derivative of the general formula (V). This is preferable because the hygroscopicity can be reduced while maintaining the property. Also,-(CH ₂ ) _n COOR ¹
Of the groups represented by, those having a smaller value of n are preferable because the glass transition temperature of the obtained hydrogenated polymer is further increased. In the above general formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, which is preferable in that the hygroscopicity of the obtained hydrogenated polymer decreases as the number of carbon atoms increases. From the viewpoint of the balance with the glass transition temperature, it is preferably a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms, and particularly preferably a methyl group, an ethyl group, or a cyclohexyl group Is preferred.

Further, the tetracyclododecene derivative of the general formula (V) wherein a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which the carboxylic acid ester group is bonded, It is preferable because the hygroscopicity is reduced without lowering the glass transition temperature of the addition polymer. In particular, the tetracyclododecene derivative of the general formula (V) in which the substituent is a methyl group or an ethyl group is preferable in that the synthesis is easy. These tetracyclododecene derivatives or a mixture of an unsaturated cyclic compound copolymerizable therewith are disclosed , for example, in JP-A-4-77520, page 4, upper right.
The thermoplastic resin used in the present invention can be subjected to metathesis polymerization and hydrogenation by the method described in column 12, line 12 to page 6, lower right column, line 6 .

In the present invention, the hydrogenated polymer used as a thermoplastic resin has an intrinsic viscosity ([η] _inh ) measured at 30 ° C. in chloroform of 0.3 to 1.5 dl.
/ G is preferable. When the [η] _inh or the weight average molecular weight is in the above range, moldability, heat resistance, water resistance, chemical resistance, mechanical properties, and the like are good. The hydrogenation rate of the hydrogenated polymer is 60 MH.
The value measured by z, ¹ H-NMR is 50% or more, preferably 90% or more, and more preferably 98% or more. The higher the hydrogenation rate, the better the stability to heat and light.

The hydrogenated polymer used as the thermoplastic resin in the present invention preferably has a gel content of 5% by weight or less, more preferably 1% by weight or less, in the hydrogenated polymer. It is particularly preferred that there is. If the gel content exceeds 5% by weight, it is not possible to prevent the occurrence of silver streaks and fish eyes on the surface of the molded product by changing any molding conditions in the injection molding. As the gel content falls below 5% by weight, these molding defects can be reduced by controlling the molding conditions of the injection molding. In particular, when the gel content is suppressed to 1% by weight or less, injection molding can be performed under severe conditions such as higher temperature and higher injection speed. When molding more precise optical parts such as CCD lids,
The gel content is 0.1% by weight or less, more preferably 0.1% by weight.
It is preferable to suppress the content to not more than 01% by weight.

As a method for obtaining such a hydrogenated polymer having a low gel content, for example, the following method can be mentioned. A method in which the finishing (removal of the solvent) process is all performed under an inert atmosphere. Since this finishing step, particularly the removal of the solvent, is performed by heating, it is desirable to operate in a nitrogen atmosphere in order to prevent gelation. Specifically, the handling of the (hydrogenated) polymer solution before entering the finishing step is all performed in a nitrogen atmosphere. Even when removing the solvent under reduced pressure,
In addition to reducing the leakage of the apparatus as much as possible, there is an operation of setting the entire apparatus under a nitrogen atmosphere so that nitrogen, instead of air, leaks even if a leak occurs.

A method in which a suitable antioxidant is added, for example, after the polymer hydrogenation step. Here, as the antioxidant that can be used to prevent the generation of a gel, a generally well-known antioxidant such as a phenol type can be applied. Specifically, pentaerythritol-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis {2 -[3- (3-t-butyl-4
-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl {2,4,8,10-tetraoxaspiro [5,5] undecane, tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, n- And octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc. These phenolic antioxidants may be used in combination with a phosphorus-based antioxidant. For example, as the phosphorus antioxidant, bis- (2,6-di-t-butyl-4)
-Methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite) and the like.

A method of lowering the temperature at the time of finishing (removing the solvent). This method includes the following methods (a) to (c). (A) A solvent having a boiling point as low as possible is used. However, when a solvent having a very low boiling point is used, during polymerization,
It is necessary to consider other factors such as an increase in the internal pressure during hydrogenation and an increase in the pressure resistance of the apparatus and an increase in the cost of the solvent itself. (B) The solvent is removed under reduced pressure. This method can be expected to be sufficiently effective. (C) An apparatus is used in which the (hydrogenated) polymer solution to be treated becomes a film as thin as possible so that the solvent can be volatilized efficiently. With the above-described method, the temperature at the time of removing the solvent is preferably kept at 300 ° C. or lower under the condition where no antioxidant is used. Also, when using an appropriate antioxidant,
It is preferable to keep the temperature at 380 ° C. or lower.

When a gel is generated by the above-mentioned method or when a gel is generated by not performing the above-mentioned method, the gel may be removed by filtration. . The generated gel is removed by filtration in the following manner. That is, the (hydrogenated) polymer is dissolved in a suitable good solvent in an amount of 20% by weight or less, preferably 15% by weight.
The solution is dissolved in a concentration of not more than% by weight, and the solution is filtered through a filter having a pore size of about 1 μm. When it is necessary to remove the gel more completely, a filter of about 0.5 μm can be used. In the present invention, any of these methods can be effectively utilized, and it is more effective to produce a hydrogenated polymer by combining these methods.

In the present invention, when the hydrogenated polymer used as a thermoplastic resin is such that the amount of water contained in the hydrogenated polymer is suppressed to 1,000 ppm or less,
Generation of silver streaks and fish eyes at the time of injection molding, peeling of the surface of the molded product, and the like are further suppressed, and more stable molding can be performed. When performing injection molding under severe conditions such as a higher temperature and a higher injection speed, good results can be obtained by controlling the water content of the hydrogenated polymer to 300 ppm or less. Further, when it is desired to perform molding stably for a long period of time, the water content of the hydrogenated polymer should be 100%.
It is desirable to keep it to below ppm. As described above, as a method for obtaining a hydrogenated polymer having a low water content, a method used for drying a general polymer, for example, a vacuum drying method, a flash drying method using dry air or dry nitrogen, or the like is used. No. In particular, when oxidation deterioration of the hydrogenated polymer is not desired, a vacuum drying method or a flash drying method using dry nitrogen is preferable.

Further, when the halogen content of the hydrogenated polymer used as the thermoplastic resin of the present invention is suppressed to 500 ppm or less, the hydrogenation Good results can be given to the generation and coloring of the coalesced gel. In particular, when the halogen content is 10
When the content is suppressed to 0 ppm or less, more preferably 50 ppm or less, better heat resistance is obtained. As a method for obtaining a hydrogenated polymer having a small halogen content, a method for obtaining a (hydrogenated) polymer using a catalyst or a solvent not containing a halogen atom (hereinafter referred to as “method”), A method in which a step for removing a halogen atom is incorporated during the production of the coalescence (for example, an extraction method and / or a method of adsorption to a hydrogenation catalyst, hereinafter referred to as a “method”).

The above method is the simplest and has a large effect because a halogen atom is not essentially incorporated into a (hydrogenated) polymer. However, the method also has problems such as that the catalyst is expensive. The catalyst used in this method includes (a) an alkoxy derivative of tungsten or molybdenum, and (b) a metathesis polymerization catalyst.
Components Combinations of an organolithium compound, an organomagnesium compound, an organozinc compound, a trialkylaluminum derivative or a tetraalkyltin compound are exemplified.
Examples of the polymerization solvent in the method include aromatic hydrocarbons such as toluene, xylene, pentane, cyclopentane, hexane, cyclohexane, and decalin; 1,2-dimethoxyethane, dimethylene glycol dimethyl ether, ether solvents such as anisole, and acetic acid. Examples include ester solvents such as methyl, ethyl acetate, propyl acetate, and butyl acetate. These polymerization solvents can be used as a mixed system.

Further, as the solvent for the hydrogenation reaction in the method, it is preferable to use all the solvents except the aromatic compounds which may be hydrogenated among the preferable solvents used in the above-mentioned polymerization. it can. On the other hand, in the extraction method in the above method, as disclosed in JP-A-2-36224, a poor solvent of a (hydrogenated) polymer is added to a (hydrogenated) polymer solution after polymerization or after hydrogenation. In addition, there is a method of recovering the (hydrogenated) polymer. When halogen atoms are removed by this extraction method, poor solvents include lower alcohols such as methanol, ethanol, and propanol; lower alcohol esters such as methyl formate, ethyl formate, methyl acetate, and ethyl acetate; and ketones such as acetone and methyl ethyl ketone. Are preferred. These poor solvents can be used in combination.

The method of adsorbing on the hydrogenation catalyst in the above-mentioned method is such that a polymer is subjected to a hydrogenation reaction using at least one metal catalyst selected from the group consisting of palladium, rhodium, ruthenium and platinum. This is a method for removing halogen atoms in the polymer. On this occasion,
The metal catalyst is preferably used by being supported on a carrier. As this carrier, carbon, silica, alumina,
Examples include silica magnesia, titania, zirconia, zeolite, and silica-alumina. The loading rate is
It is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0.2 to 7% by weight. Among these metal catalysts, palladium is particularly preferred because of its high chlorine removal rate. As the carrier, alumina, silica, and silica magnesia are preferable from the viewpoint of specific gravity, catalyst, and ease of preparation. For details of the method of adsorbing on the hydrogenation catalyst, see JP-A-3-107904 (Japanese Patent Application No.
244659) .

It is particularly preferable that the thermoplastic resin used in the present invention comprises a hydrogenated polymer obtained by hydrogenating the above-mentioned norbornene-based polymer. It can be further stabilized by adding an agent or the like. Also, to improve workability,
Additives used in conventional resin processing, such as lubricants, can also be added.

Next, the above-mentioned norbornene skeleton is provided.
A method for molding the CCD lid of the present invention using an organic polymer material made of a thermoplastic resin will be described. First, if necessary, a thermoplastic resin is mixed or mixed with a stabilizer such as a ribbon blender, a tumbler blender, and a Henschel mixer together with other stabilizers and additives such as an antistatic agent in an amount that does not impair the effects of the present invention. , Melt-mixing with a Banbury mixer, two rolls, etc., or dissolved in a hydrocarbon or aromatic solvent and mixed in the state of a polymer solution, then a single screw extruder, a vented extruder, a twin screw extruder, Injection using a triple screw extruder, conical twin screw extruder, co-kneader, plasticizer, mixed caterer, twin screw conical screw extruder, planetary screw extruder, gear extruder, screwless extruder, etc. Molding is performed, and molding is performed using a mold for molding a lid for CCD. That is, an appropriate amount of resin melt-plasticized uniformly by a screw in a heating cylinder of these extruders is injected and held in a mold at a high speed and solidified by cooling. In addition, the CCD lid can be formed by injection compression molding, press molding, extrusion molding, solution casting molding, or the like.

When the CCD lid of the present invention has poor adhesion to ceramics (for example, when the organic polymer material is a polyolefin and a norbornene-based polymer is used), the adhesion side of the lid is changed. Adhesion can be improved by forming a thin film on the surface by a technique such as sputtering, vapor deposition, or wet coating. Further, in order to further improve the water absorption resistance and the adhesion, one or both surfaces of the CCD lid can be subjected to a surface treatment by the same method.

The CCD lid thus obtained can be adhered to the base ceramic using an arbitrary adhesive. It is necessary to select an adhesive that strongly adheres both the lid material and the ceramic and that does not peel off due to a difference in the coefficient of thermal expansion due to thermal cycling. In this case, in order to improve the adhesiveness, an inorganic film or an organic film may be previously adhered to the adhesion surface of the lid by a method such as sputtering or coating to adhere. Examples of the adhesive include hot melt adhesives such as ethylene-vinyl acetate copolymer, polyamide, polyester, and thermoplastic rubber, and various additives to the base polymer such as a plasticizer, an antioxidant, and a tackifier. In addition to rosin, terpene resin, petroleum resin, and the like, a cyanoacrylic adhesive, an epoxy adhesive, a polyurethane adhesive, an ultraviolet curable adhesive, and the like can be used. Epoxy adhesives are often used because of their excellent adhesion of inorganic materials. An epoxy resin, a curing agent, a curing accelerator, a diluent, a filler, and the like are compounded in the epoxy adhesive. As the epoxy resin, bisphenol A glycidyl ether, tetrabromobisphenol A, novolak type epoxy resin, bisphenol F type epoxy resin, tetraglycidylaminodiphenylmethane, trifunctional or tetrafunctional epoxy resin for improving heat resistance and the like are used. As a curing agent, a curing agent used for a two-pack type such as polyamine, polysulfide, polysulfide / tertiary amine epoxy polyamide, dicyandiamide, dicarboxylic dihydrazide, microencapsulated amine, moisture-decomposable ketimine, BF ₃ .amine complex And a one-pack type latent curing agent such as an amine imide. For bonding between inorganic and organic materials, use epoxy resin mixed with nitrile rubber, modified nitrile rubber such as acid copolymerized nitrile rubber, various rubbers such as chloroprene rubber, or compounded with organic materials. To improve adhesion.

As the UV-curable adhesive, acrylates are mainly used, and specific examples thereof include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, and other higher alkyls. Monofunctional acrylate monomers such as acrylate; other monofunctional monomers such as vinylpyrrolidone; two or more polyols such as ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, hexanediol, trimethylolpropane, and pentaerythritol Examples thereof include polyfunctional acrylate monomers to which acrylate is bonded. The reactive oligomers contained therein include polyester acrylate having an acryloyl group at the terminal, epoxy acrylate or polyurethane acrylate having an epoxy group in the molecular chain and an acryloyl group at the terminal, and unsaturated unsaturated compound having a double bond in the molecular chain. Examples include polyester, 1,2-polybutadiene, and other oligomers having an epoxy group or a vinyl ether group.

As the photopolymerization initiator, benzophenone,
Examples thereof include methyl orthobenzoyl benzoate, benzoin alkyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, chlorinated acetophenone, and α-acyloxime ester. When irradiated with ultraviolet light, radical polymerization of these reactive monomers and / or reactive oligomers is initiated or promoted by a photopolymerization initiator, and the resin is cured, whereby adhesive performance is exhibited. Further, an appropriate solvent or a thermoplastic polymer may be added for the purpose of adjusting the viscosity or improving the adhesive strength. In addition, the substrate of the CCD is generally made of ceramics, but epoxy resin,
Synthetic resin such as silicone epoxy resin, phenol resin, diallyl phthalate resin, alkyd resin, polyphenylene sulfide resin, etc. as the main agent, electrical insulation, mechanical strength, increase of heat deformation temperature, improvement of thermal conductivity, adjustment of coefficient of thermal expansion Novolak glycidyl ether type phenolic curing agent, curing accelerator, fused silica filler, silane coupling agent, flame retardant, coloring agent, release agent, etc. A resin composition,
With the same main component as the lid, a novolak glycidyl ether type phenolic curing agent, a curing accelerator, a fused silica filler, a silane coupling agent, a flame retardant, a coloring agent, a release agent, etc. were compounded for the purpose of improving the above properties. Using insert molding, injection molding, transfer molding,
It is made by molding according to the resin, such as drop casting. Among them, it is preferable to use the same material as the lid material in terms of adhesiveness and durability. This can be made by molding with the same material as the lid, so that the adhesiveness can be stabilized.

By the way, conventionally, an image or information projected on a CCD is read through a glass lid. Also,
At this time, human eyes or sensors often read this information through a lens. Conventionally, a glass lid is flat on both sides due to its workability. However, since the lid for CCD of the present invention is made of an organic polymer material, the lid can be formed by injection molding, so that a spherical or aspherical lid can be easily manufactured. If such processing is applied to the CCD lid, the number of lenses can be reduced in a device using the CCD, which leads to a reduction in size at once. Therefore, the CCD lid of the present invention can have a lens function by making both surfaces or one surface spherical or aspherical. It is also conceivable that the bar is captured by a bar coder or the like, or the bar is reduced in size, which is effective for giving the lid an enlargement function. The structure of the lens differs depending on the application, but it should be a convex lens for enlargement, and an aspherical surface designed to keep the magnification between the center and the end constant or to reduce the difference. preferable.

[0037]

The lid for CCD of the present invention has the above-mentioned physical properties.
Because it uses an organic polymer material made of a thermoplastic resin having a norbornene skeleton , injection molding, extrusion molding,
It can be easily molded by generally known molding methods such as press molding and exhibits excellent performance as a lid for CCD. In addition, the strength can be maintained and the thickness can be reduced as compared with the glass lid, and both sides or one side of the lid can be easily processed into a spherical surface or an aspherical surface.
It is possible to cope with miniaturization and weight reduction of a device using a CD itself.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified. Various measurements in the examples are as follows. Intrinsic viscosity ([η] _inh ) Using chloroform as a solvent, the viscosity was measured with an Ubbelohde viscometer at 30 ° C. at a polymer concentration of 0.5 g / dl. Hydrogenation rate In the case of hydrogenated homopolymer, 60 MHz, ¹ H-NMR
Was measured. The glass transition temperature was measured by a scanning calorimeter (DSC) at a heating rate of 10 ° C./min in a nitrogen atmosphere.

The heat distortion temperature was measured under the conditions of ASTM D648 and 18.6 kgf / cm ² . The light transmittance was measured in the range of 400 nm to 900 nm, and the lowest value in the range was shown. Photoelastic coefficient was measured by an ellipsometer. Image brightness, distortion Visual comparison with commercially available glass Image brightness; 同等 Equal to or higher than glass ○ Slightly inferior to glass, but no problem in practical use Image distortion; い な い No distortion at all. ○ Although there is some distortion, there is no problem in practical use. Saturated water absorption: 20 days, weight increase rate when kept at 50 ° C x 95% humidity. Crack test Place the board on a flat surface and examine cracks when pressed with fingers. Was. ◎ Does not break. × Crack.

Fogging after the moisture resistance test The CCD was kept at 50 ° C. and 95% humidity for 20 days, then returned to room temperature and visually inspected for fogging inside the CCD lid. ◎ There is no fogging. ○ There is slight cloudiness, but there is no practical problem. △ Somewhat cloudy. Adhesion to Ceramics A lid for a CCD was adhered with a commercially available ultraviolet-curable resin and peeled off with a nail. ◎ It does not come off at all. ○ It hardly peels off, but partly peels off when scratched strongly. △ Partly peeled off.

Reference Example 1 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene 10
0 g, 60 g of 1,2-dimethoxyethane, 240 g of cyclohexane, 25 g of 1-hexene, and 3.4 ml of a toluene solution of 0.96 mol / l of diethylaluminum chloride were added to an autoclave having a content volume of 1 liter. On the other hand, in another flask, a 0.05 mol / l solution of tungsten hexachloride in 1,2-dimethoxyethane 20 was added.
ml and 10 ml of a 0.1 mol / l 1,2-dimethoxyethane solution of paraaldehyde were mixed. 4.9 ml of this mixed solution was added to the mixture in the autoclave. After sealing, the mixture was heated to 80 ° C. and stirred for 3 hours. To the obtained polymer solution, a mixed solvent of 2/8 (weight ratio) of 1,2-dimethoxyethane and cyclohexane was added to make the polymer / solvent 1/10 (weight ratio), and then 20 g of triethanolamine was added. Was added and stirred for 10 minutes.

To this polymerization solution, 500 g of methanol was added, and the mixture was stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was further repeated twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane to obtain a cyclohexane-1,2-dimethoxyethane solution having a polymer concentration of 10%. 20 g of palladium / silica magnesia (manufactured by Nikki Chemical Co., Ltd., palladium amount = 5%) was added to this solution, and hydrogen pressure was set to 40 in an autoclave.
After the reaction at 165 ° C. for 4 hours at kg / cm ² , the hydrogenation catalyst was removed by filtration to obtain a hydrogenated polymer solution.
Further, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added to this hydrogenated polymer solution.
After 0.1% was added to the hydrogenated polymer, the solvent was removed at 380 ° C under reduced pressure. Next, the molten resin was pelletized by an extruder under a nitrogen atmosphere, and an intrinsic viscosity of 0.5 dl / g (30 ° C. in chloroform) and a hydrogenation rate of 9 were obtained.
A 9.5% thermoplastic resin having a glass transition temperature of 168 ° C. was obtained.

Reference Example 2 6-ethylidene-2-tetracyclododecene was subjected to metathesis ring-opening polymerization in the same manner as in Reference Example 1, then hydrogenated and pelletized to obtain an intrinsic viscosity of 0.56 dl / g (30 ° C., A thermoplastic resin having a degree of hydrogenation of 99% and a glass transition temperature of 140 ° C. was obtained.

Examples 1 to 4 and Comparative Examples 1 to 4 Thermoplastic resin pellets obtained in Reference Examples 1 to 2, polycarbonate (PC, manufactured by Teijin Chemicals Limited), polymethyl methacrylate [PMMA, Mitsubishi Rayon Acrylic resin [Hitachi Chemical Co., Ltd.]
Using an injection molding machine manufactured by Meiki Seisakusho Co., Ltd. as a raw material to obtain plates having an area of 1 cm ² . The physical properties and the evaluation as a CCD when the plate was attached to ceramics are shown in Tables 1 and 2. The physical properties of commercially available glass lids for CCD are also shown as comparative examples .

Example 5 On one side of the plate made of the thermoplastic resin of Reference Example 1 used in Example 1, the thermoplastic resin of Reference Example 2 having a saturated water absorption of 0.01% having a thickness of 0.01 mm was applied. The film was coated with a toluene solution so as to form a film and dried quickly to obtain a sheet having a thin film of the thermoplastic resin of Reference Example 2. When the test was performed in the same manner as in Example 1, no fogging occurred after the moisture resistance test.

Example 6 The film of Reference Example 1 was adhered to one side of the thermoplastic resin plate of Reference Example 2 used in Example 2 in the same manner as in Example 5 . When the film side made of the thermoplastic resin of Reference Example 1 was adhered to ceramics, the adhesion was improved as in Example 1.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

According to the present invention, the workability and workability, which are the drawbacks of the conventional glass lid, are improved.
It is possible to provide a lid that maintains the heat resistance, optical properties, low water absorption, etc., which are the characteristics of glass at a practical level, as well as to reduce the weight and size of equipment.
A lid for a CD can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-195065 (JP, A) JP-A-2-103226 (JP, A) JP-A-3-122105 (JP, A) 21580 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01L 27/14 C08F 32/00 C08G 61/08 H01L 23/02

Claims (2)

(57) [Claims] 1. A heat deformation temperature of 70 ° C. or more and a wavelength of 400 n
The light transmittance from m to 900 nm is 80% or more, the absolute value of the photoelastic coefficient is 10 ⁻¹⁰ cm ² / dyne or less, and the saturated water absorption is 2% by weight or less, and the following general formulas (I) to (I) IV) A CCD lid made of an organic polymer material having at least one kind of norbornene skeleton represented by the following formula: Embedded image Embedded image Embedded image Embedded image [Wherein A, B, C and D represent a hydrogen atom, a carbon number of 1 to
10 hydrocarbon groups, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom,-(CH ₂ ) _n C
_{^{OOR 1, - (CH 2)}} n OCOR 1, - (CH 2) n
OR ¹ ,-(CH ₂ ) _n CN,-(CH ₂ ) _n CONR
_{^{3 R 2, - (CH 2}} ) n COOZ, - (CH 2) n OC
OZ,-(CH ₂ ) _n OZ,-(CH ₂ ) _n W, or composed of B and C Or a (poly) cyclic alkylene group. Here, R ¹ , R ² , R ³ and R ⁴ have 1 to 2 carbon atoms.
0 hydrocarbon group, Z is a hydrocarbon group substituted with a halogen atom, W represents _{^{SiR 5 p F 3-p (}} R 5 is a hydrocarbon group having 1 to 10 carbon atoms, F is a halogen atom, -OCOR ⁶ or −
OR ⁶ (R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms),
p represents an integer of 0 to 3), and n represents an integer of 0 to 10. ] 2. The CCD lid according to claim 1, wherein at least one surface is spherical or aspherical.