WO1998020560A1 - Materiau plastique pour fermer un boitier d'element de prise de vue a semi-conducteur, et procede de fabrication associe - Google Patents

Materiau plastique pour fermer un boitier d'element de prise de vue a semi-conducteur, et procede de fabrication associe Download PDF

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Publication number
WO1998020560A1
WO1998020560A1 PCT/JP1997/004021 JP9704021W WO9820560A1 WO 1998020560 A1 WO1998020560 A1 WO 1998020560A1 JP 9704021 W JP9704021 W JP 9704021W WO 9820560 A1 WO9820560 A1 WO 9820560A1
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Prior art keywords
component
solid
diisocyanate
meth
imaging device
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PCT/JP1997/004021
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English (en)
Japanese (ja)
Inventor
Katsuichi Machida
Takeo Ogihara
Masuhiro Shouji
Hiroki Katono
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Kureha Kagaku Kogyo Kabushiki Kaisha
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Publication of WO1998020560A1 publication Critical patent/WO1998020560A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0203—Containers; Encapsulations, e.g. encapsulation of photodiodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates to a plastic lid material for a solid-state imaging device package comprising an acrylic cross-linked copolymer and a method for producing the same.
  • glass has been used as a lid material (window material) for sealing a CCD or other solid-state image sensor.
  • glass materials have high specific gravity and are brittle against impact.
  • the glass material may be damaged when handling the glass material or when performing a cutting process, so that a high yield cannot be obtained. Post-processing is necessary because it is easy to occur, and these are factors that increase manufacturing costs.
  • the present invention has been made in view of the circumstances described above, and a first object of the present invention is to have a low specific gravity, moldability, transparency, adhesive toughness, dimensional stability, and solvent resistance.
  • An object of the present invention is to provide a plastic lip material for a solid-state imaging device package which is excellent in heat resistance and mechanical properties.
  • a second object of the present invention is to provide a method capable of advantageously producing the above-mentioned plastic lid material for a solid-state imaging device package having an optical one-pass filter function. Is to provide.
  • the plastic lid material for a solid-state imaging device package of the present invention is obtained by subjecting the following component (A), the following component (B), and the following component (C) to a urethanation reaction and a radical polymerization reaction. It is characterized by comprising an acrylic cross-linked copolymer.
  • the plastic lid material for a solid-state imaging device package of the present invention has a (meth) acryl having a urethane bond obtained by a urethanization reaction between the following component (A) and the following component (B). It is characterized by comprising an acrylic cross-linked copolymer obtained by subjecting an acid ester compound and the following component (C) to a radical polymerization reaction.
  • (A) Component (meth) acrylic acid ester monomer having a secondary hydroxyl group.
  • (B) Ingredient: dicyclohexylmethane 1,4'-diisocyanate, isophorone diisocyanate and at least one diisocyanate compound selected from 1,3_bis (isocyanatomethyl) cyclohexane.
  • Component (C) a monomer capable of being radically copolymerized with the component (A).
  • plastic lid material for a solid-state imaging device package of the present invention it is preferable to use a (meth) acrylic acid ester compound having a glycidyl group as a part or all of the component (C).
  • dicyclohexylmethane-1,4′-diisocyanate as a part or the whole of the component (B).
  • the number of moles of hydroxyl groups derived from the (meth) acrylic acid ester monomer having a secondary hydroxyl group is represented by a
  • the number of hydroxyl groups derived from dicyclohexylmethane-1,4'-diisocyanate is represented by a.
  • the number of moles is b and the number of moles of isophorone group derived from isophorone diisocyanate and Z or 3-bis (isocyanomethyl) cyclohexane is c, the following conditions (1) ) And condition (2) are preferably satisfied.
  • Condition (1) 0.8 ⁇ (b + c) / a ⁇ l.2.
  • Condition (2) 0 ⁇ c / (b + c) ⁇ 0.85.
  • a diffraction grating having an optical low-pass filter function may be formed on the surface, and an optical aperture-pass filter function may be formed on the surface.
  • Diffraction grating layers may be laminated.
  • an optical multilayer film for selectively reducing transmission or reflection of a light beam in a specific wavelength range may be formed on the surface.
  • the method for manufacturing a plastic lid material for a solid-state imaging device package includes the steps of: forming at least one mold plate having a negative pattern of a diffraction grating formed on one surface thereof; By arranging them so as to face each other, a cavity is formed, and a (meth) acrylate having a urethane bond obtained by a urethanization reaction between the component (A) and the component (B) within the cavity.
  • primary hydroxyl group refers to a hydroxyl group bonded to a primary carbon atom.
  • primary carbon atom refers to a carbon atom that is bonded to only one other carbon atom.
  • second hydroxyl group refers to a hydroxyl group bonded to a secondary carbon atom.
  • secondary carbon atom refers to a carbon atom bonded to two other carbon atoms.
  • Tertiary hydroxyl group refers to a hydroxyl group bonded to a tertiary carbon atom.
  • tertiary carbon atom refers to a carbon atom bonded to three other carbon atoms.
  • (meth) acrylic acid” means “acrylic acid” Or “methacrylic acid” and "(meth) acrylate” means “acrylate” or "methacrylate”.
  • the figure is a curve diagram showing the spectral transmission characteristics of the lid material according to one embodiment of the present invention.
  • the present invention will be described in detail.
  • the plastic lid material for a solid-state imaging device package comprises a component (A) composed of a specific (meth) acrylic acid ester monomer and a component (B) composed of a specific diisocyanate compound.
  • the component (A) and the component (C) comprising a monomer capable of undergoing radical copolymerization with the component (A) from an acryl-based cross-linked copolymer obtained by a urethanization reaction and a radical polymerization reaction. It becomes.
  • the specific (meth) acrylate monomer used as the component (A) has a secondary hydroxyl group.
  • a specific (meth) acrylic acid ester-based monomer By using such a specific (meth) acrylic acid ester-based monomer, a crosslinked copolymer having high heat resistance and high transparency can be obtained.
  • (meth) acrylic acid ester monomer having a secondary hydroxyl group examples include 2-hydroxypropyl (meth) acrylate and 2-hydroxyhydroxy (meth) acrylate.
  • Relate 2 hydroxy-1,3,3-di (meth) acryloxypropane, 2 methoxyloxyshethyl-2—hydroxypropyl phthalate, 2—hydroxy—3—acryloxypropylmethacrylate Tactylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3 phenoxypropyl (meta) acrylate, and the like.
  • a (meth) acrylic acid ester-based monomer for obtaining a crosslinked copolymer for example, one having a primary hydroxyl group such as 2-hydroxyxyl methacrylate is used, high heat resistance is required.
  • a cross-linked copolymer having hydrophilicity cannot be obtained, and depending on the type of the component (B) or the component (C), which will be described later, it becomes cloudy in the urethanization reaction or the radical polymerization reaction. No copolymer is obtained.
  • a (meth) acrylate monomer having a tertiary hydroxyl group is used.
  • the tertiary hydroxyl group and the isocyanate group of the diisocyanate compound described below do not sufficiently proceed due to steric hindrance, so that the resulting cross-linked copolymer contains an isocyanate group. Remains at a high rate. As a result, the weather resistance and storage stability of the obtained cross-linked copolymer are reduced, and the releasability is remarkably reduced due to the reaction with the glass constituting monolide in the casting polymerization. Occurs.
  • the specific diisocyanate compound used as the component (B) is dicyclohexylmethane-1,4,4'-diisocyanate, isophorone diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane It is at least a kind of dissociated compound selected from By using such a specific diisocyanate compound, a crosslinked copolymer having high heat resistance, excellent weather resistance, and high mechanical strength (flexural modulus) can be obtained.
  • a diisocyanate compound other than the above specific diisocyanate compound for example, 1,6-hexanediisocyanate
  • a crosslinked copolymer having high heat resistance and high mechanical strength is used. Can not get.
  • Dicyclohexylmethane 1,4,4'-diisocyanate, isophorone diisocyanate, and 1,3_bis (isocyanonemethyl) cyclohexane may be used alone or in combination as the component (B). Since the cross-linked copolymer obtained when isophorone diisocyate or 1,3-bis (isocyano-methyl) cyclohexane alone is used alone is liable to be brittle, It is preferable to use dicyclohexylmethane-1,4,4'-diisocyanate as a part or all of the component (B).
  • the number of moles of the hydroxyl group derived from the (meth) acrylic acid ester monomer having a secondary hydroxyl group used as the component (A) is defined as a
  • the dicyclohexylmethane used as the component (B) is defined as a
  • the molar number of the isocyanate group derived from 4,4'-diisocyanate is defined as b, isophorone diisocyanate used as component (B) and Z or 1,3-bis (isocyanatemethyl) cyclohexane
  • the value of (b + c) 3 is 0.8 or less, a high proportion of the isocyanate group remains in the obtained cross-linked copolymer. In some cases, the mold reacts with the glass constituting the mold to significantly reduce the releasability, or the weather resistance and the stability over time may be reduced. On the other hand, when the value of (b + c) / a is 1.2 or more, a high ratio of hydroxyl groups remains in the obtained cross-linked copolymer, so that the cross-linked copolymer has hydrophilicity and water absorption. It tends to be expensive.
  • the component (C) is a monomer capable of radical copolymerization with the (meth) acrylic acid ester-based monomer having a secondary hydroxyl group as the component (A) (hereinafter referred to as “radical copolymerizable monomer”). It is also called.
  • radical copolymerizable monomers include both monofunctional ones having one radically polymerizable double bond and polyfunctional ones having two or more radically polymerizable double bonds. Can be used.
  • the monofunctional radical copolymerizable monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and tert-butyl.
  • Lower alkyl (meth) acrylates having 1 to 8 carbon atoms in the alkyl group such as (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate ) Acrylates, phenyl (meth) acrylates, etc.
  • aromatic groups (methyl) acrylates, methoxethyl (meta) acrylate, butoxyl (meth) acrylate (Meth) acrylate, isobornyl (meth) acrylate having a lower alkyl group via ethylenoxide such as relay and diethylene glycol mono (meth) acrylate Isobornyl group (Meth) acrylate having an alkyl group substituted with styrene, styrene, ⁇ -methylstyrene, divinylbenzene, p-ter (A) aromatic vinyl compounds such as monobutylstyrene, glycidyl (meth) acrylate, and (meth) acrylates having a glycidyl group such as methyldaricidyl (meth) acrylate; Can be
  • polyfunctional radical copolymerizable monomer examples include ethylene glycol (meth) acrylate, polyethylene glycol (meta) acrylate, and 1,4-butarene.
  • Multifunctional (meth) acrylates such as propane, pen erythritol and tetra (meth) acrylate Can be
  • a (meth) acrylate having a glycidyl group as a part or all of the component (C), and the proportion of the component (A), the component (B), and the component (C) It is preferably 130% by mass of the total amount of the components.
  • the acrylic cross-linked copolymer constituting the plastic lid material for a solid-state imaging device package of the present invention comprises the above component (A), component (B), and component (C). It is obtained by a rethanation reaction and a radical polymerization reaction.
  • a perethane-forming reaction catalyst and a radical polymerization initiator are added to a monomer mixture comprising the three components (A), (B) and (C), and the perethane-forming reaction is carried out under appropriate conditions.
  • the acrylic-based cross-linked copolymer can be produced by simultaneously proceeding with the lacquer polymerization reaction.
  • the components (A) and (B) are allowed to undergo urethanization reaction in the presence of a urethanization reaction catalyst from the viewpoints of low shrinkage and good mold release properties from the glass mold.
  • a solution containing a radical polymerization initiator (hereinafter, referred to as a “radical polymerizable solution”) is prepared, and the radical polymerizable solution is subjected to a polymerization treatment to obtain an acrylic cross-linked copolymer. It is preferred to manufacture.
  • the urethane bond-containing prepolymer is obtained by adding a urethanization reaction catalyst to a mixture comprising the components (A) and (B) and subjecting the components (A) and (B) to a urethanization reaction under appropriate conditions. It is also possible to manufacture by.
  • the urethane bond-containing prepolymer obtained is a considerably viscous liquid or solid, in preparing a radical polymerizable solution, the urethane bond-containing prepolymer is used as a radical copolymerizable monomer as the component (C). It may be difficult to fully dissolve in the monomer.
  • reaction product solution a solution in which the urethane bond-containing prepolymer as the reaction product is dissolved in the component (C) (hereinafter, referred to as “reaction product solution”) is obtained.
  • the urethanization reaction when performing the urethanization reaction between the component (A) and the component (B), it is not necessary to use all of the component (C), and the urethanization reaction is performed using a part of the component (C). Thereafter, the remaining component (C) may be added to the reaction product solution.
  • urethanization reaction catalyst a commonly used amine catalyst, metal salt catalyst, organometallic catalyst, etc. can be used, but the specific (meth) acrylic acid ester constituting the component (A) can be used.
  • the secondary hydroxyl group of the monomer is not so highly reactive with the specific group of the specific compound constituting the component (B). It is preferable to use a highly active organotin catalyst such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate and the like.
  • the urethanization reaction between the component (A) and the component (B) can be carried out at the same reaction temperature and reaction time as in a normal urethanization reaction.
  • a radical polymerization initiator By adding a radical polymerization initiator to the reaction product solution thus obtained, a radically polymerizable solution can be prepared.
  • radical polymerization initiator an ordinary organic peroxide-based polymerization initiator can be used, but tert-butyl butoxy neodecanoate is used because the degree of coloring of the obtained crosslinked copolymer is small.
  • Non-aromatic carboxylic esters such as tert-butyl butyl oxyvalate, tert butyl butyl 2-ethylhexanoate, tert-butyl propyl laurate, etc .; It is preferable to use a dicarboxylic acid such as an oxide.
  • 2,2'-azobis isobutyronitrile
  • 1,2,3-diazobis cyclohexane-2-carbonitrile
  • the azo radical polymerization initiator of the above can also be suitably used.
  • an antioxidant an ultraviolet absorber, a light stabilizer, and other additives can be added to the radical polymerizable solution as needed.
  • the ratio of the urethane bond-containing prepolymer to the component (C) in the radical polymerizable solution is preferably such that the urethane bond-containing prepolymer and the component (C) are in a mass ratio of 80:20 to 20:80. .
  • the sealing material may be dissolved at the time of casting polymerization described below.
  • the proportion of the urethane bond-containing prepolymer is too large, the viscosity of the radically polymerizable solution becomes too high, which makes it difficult to obtain an acryl-based crosslinked copolymer by casting polymerization.
  • the acrylic cross-linked copolymer constituting the plastic liz material for the solid-state imaging device package of the present invention is obtained. can get.
  • the specific method of the polymerization treatment is not particularly limited, and a radical polymerization method using a usual polymerization initiator can be employed.However, the obtained acryl-based crosslinked copolymer is not melt-molded. Since it is difficult, it is preferable to use a casting polymerization method in which a molded product is directly obtained.
  • an acryl-based crosslinked copolymer is obtained by a casting polymerization method
  • a cavity is formed by enclosing, and a monomer mixture containing a radical polymerization initiator is injected into the cavity, and the monomer mixture is heated or irradiated with light to copolymerize the monomer mixture.
  • a sheet-like or plate-like molded product made of a cryl-based crosslinked copolymer is obtained.
  • a molded article composed of an acryl-based crosslinked copolymer having an optical surface on the surface can be obtained by copolymerizing a urethane bond-containing prepolymer and a component (C) in a radical polymerizable solution. It can be obtained directly, and a lid material can be obtained by cutting the molded body as necessary. Therefore, a surface polishing step, which is an essential step for forming an optical plane in the production of a conventional glass lid material, is not required, so that the lid material can be easily produced.
  • the sealing material is made of a solvent-resistant material, for example, a fluorine-based rubber.
  • a gasket comprising: (C) component, since the urethane bond-containing prepolymer is dissolved in the component (C), the erosion property of the component (C) is reduced. It is not necessary to use a material made of a material having high solvent resistance. For example, a material made of silicone rubber can be used.
  • the radical polymerization reaction between the urethane bond-containing prepolymer and the component (C) is as follows.
  • the reaction can be carried out at the same reaction temperature and the same reaction time as the ordinary radical polymerization reaction.
  • the molded article made of the acrylic cross-linked copolymer thus obtained has a specific gravity of 1.0 to 1.5 and a thickness of 0.1 to 2 mm in a sheet or plate shape. Visible light transmittance of 80% or more, flexural modulus of 300 MPa or more, heat resistance temperature (bit softening point, load 5 kg) of 130 ° C or more, water absorption Have a performance of 3% or less.
  • it does not substantially contain a substance that emits radiation such as ⁇ rays, and is extremely suitable as a lid material for a solid-state imaging device package.
  • a diffraction grating having an optical aperture filter function can be provided on the surface.
  • a lid material is used for a solid-state imaging device package of a solid-state imaging device that requires an optical low-pass filter function for removing high spatial frequency components of subject light and preventing generation of a false signal. It is suitable as.
  • the above-mentioned diffraction grating having an optical low-pass filter function may be provided by directly forming on the surface of the above-mentioned molded article made of the acrylic cross-linked copolymer, and may be formed by diffraction on the surface of the molded article. It may be provided by laminating a lattice layer.
  • a negative pattern of the diffraction grating is formed on at least one surface (the inner surface) of at least one of a pair of mold plates in the casting polymerization method described above.
  • the negative pattern of the diffraction grating is formed on the surface of the molded body.
  • a film on which a diffraction grating is formed (hereinafter referred to as a “diffraction grating film”) is prepared, and this diffraction grating film is used as a molded body. There is a method of laminating and bonding.
  • a heat-curable or light-curable adhesive or pressure-sensitive adhesive is used.
  • an adhesive or a pressure-sensitive adhesive a heat-curable or light-curable adhesive or pressure-sensitive adhesive is used.
  • an epoxy-based, urethane-based or acryl-based adhesive, or an acrylic-based adhesive excellent in transparency and weather resistance can be preferably used.
  • a hard coat layer, an anti-reflection layer, and the like can be formed on the surface of the plastic lid material for a solid-state imaging device package of the present invention by post-processing.
  • an optical multilayer film similar to that usually formed on a glass substrate on the liz material of the present invention, a light beam in a specific wavelength range is utilized by utilizing the interference action of the optical multilayer film. It is also possible to provide a filter function for reducing the transmittance of the stencil.
  • the optical multilayer film usually has a low refraction with a thickness corresponding to the optical path length of 1 Z 4 of the light wavelength for the purpose of selectively reducing transmission or reflection of light in a specific wavelength range on the surface of the substrate material.
  • the thin film such as a rate which is the material of silicon oxide (S i 0 2) titanium oxide thin film and a high refractive index material such as (T i 0 2), a thin film-shaped formation method such as vacuum deposition Ya sputtering-ring method It is formed by alternately laminating the substrates, but when this method is performed, the temperature of the substrate increases spontaneously, and the substrate is actively heated to improve film forming properties. In some cases, the substrate needs to be made of a material having excellent heat resistance.
  • the lid material of the present invention has extremely excellent heat resistance. Therefore, when a thin film is formed on the surface of the lid material by a vapor deposition method, a conventional material having low heat resistance is used. Sufficiently excellent film-forming properties can be obtained as compared to the rill resin, and therefore, an optical multilayer film having a large number of thin film layers can be formed with high reliability and sufficient adhesion to a substrate.
  • the optical multilayer film can be formed of a metal or a metal salt, an inorganic oxide, an inorganic sulfide, or the like.
  • parts means “parts by mass”.
  • A is the number of moles derived from a (meth) acrylic acid ester monomer having a secondary hydroxyl group
  • b is derived from dicyclohexylmethane-4,4′-diisocyanate.
  • the number of moles of the isocyanate group, “c”, represents the number of moles of the isocyanate group derived from isophorone diisocyanate and / or 1,3 bis (isosinate methyl) cyclohexane.
  • reaction product solution After cooling the obtained reaction product solution to room temperature, polymerization reaction A radically polymerizable solution was prepared by adding 1.0 part of tel-t-butylhydroxyl-2-ethylhexanoate as an initiator.
  • a pair of glass mold plates each having an optical plane on one side and measuring 100 mm x 100 mm x 5 mm are arranged at 1 mm intervals so as to face each other.
  • a cavity was formed between each mold plate by surrounding the side surface of the mold plate with a seal material made of a silicone rubber gasket having a thickness of l mm and a width of 5 mm.
  • This molded product was cut into a size of 9 mm ⁇ 9 mm to obtain a plastic lip material for a solid-state imaging device package of the present invention.
  • the Vicat softening point temperature was measured in accordance with the JISK 7206B method. If the Vicat softening point temperature exceeds 150 ° C, the displacement at 150 ° C was measured. Was.
  • the epoxy composite package material and the lid material are adhered to each other with an epoxy-based thermosetting adhesive, and held at 0 to 150 ° C for 2 to 4 hours while fixed with a jig. After cooling the lid material, observe the lid material, and mark it as “ ⁇ ” if no crack or deformation has occurred, and “X” if there is poor bonding, cracking or deformation. evaluated.
  • the radical polymerizable solution is added to the reaction product solution by adding 0.8 part of tert-butyl benzopivalate as a polymerization initiator. Prepared.
  • the prepared radically polymerizable solution was poured into the cavity formed in the same manner as in Example 1, and the temperature was adjusted to 40 ° C for 10 hours, 65 ° C for 4 hours, 80 ° C for 1 hour, and 100 ° C.
  • the radical polymerizable solution is polymerized by heating at a temperature different from that for 1 hour in order to produce a colorless and transparent plate-like molded article of 0.9 mm thick made of an acrylic cross-linked copolymer. Obtained.
  • the molded body was cut into a size of 9 mm X 9 mm to produce a plastic lid material for a solid-state imaging device package of the present invention, and the evaluation was performed in the same manner as in Example 1. .
  • Table 1 shows the results.
  • a radical polymerizable solution is added to the reaction product solution by adding 1.0 part of tert-butylvinyl-2-ethylhexanoate as a polymerization initiator.
  • a radical polymerizable solution is added to the reaction product solution by adding 1.0 part of tert-butylvinyl-2-ethylhexanoate as a polymerization initiator.
  • a pair of circular glass mold plates each having an optical plane on one side, a thickness of 5 mm, and a diameter of 120 mm, are placed opposite each other at 1.1 mm intervals.
  • the side of the board is made of an adhesive tape with a silicone-based adhesive layer.
  • a cavity was formed between each of the mold plates by enclosing with a sealing material, and the prepared radically polymerizable solution was poured into the cavity, and the solution was heated at 48 ° C for 10 hours at 65 ° C. 4 hours, 90 hours for 1 hour, and 120 hours for 1 hour at different temperatures to carry out the polymerization of the radically polymerizable solution to reduce the thickness of the acrylic bridge copolymer.
  • a 1.0 mm colorless and transparent plate-like molded product was obtained.
  • the molded body was cut into a size of 9 mm X 9 mm to produce a plastic lid material for a solid-state imaging device package of the present invention, and the evaluation was performed in the same manner as in Example 1. .
  • Table 1 shows the results.
  • reaction product solution After cooling the obtained reaction product solution to room temperature, this reaction product solution was added with 10 parts of glycidyl methacrylate [component (C)], and ethyl 2-cyano 3, 3- as an ultraviolet absorber. Add 0.2 parts of diphenylacrylate and 1.2 parts of 1,1-azobis (cyclohexane-12-carbonitrile) as a polymerization initiator Thus, a radical polymerizable solution was prepared.
  • a cavity was formed in the same manner as in Example 3 except that a pair of mold plates was arranged at an interval of 0.9 mm, and the prepared radically polymerizable solution was poured into the cavity, and the solution was poured with 68 to 1 0 hours, 8 five.
  • the thickness of the acrylic cross-linked copolymer becomes 0.8 mm.
  • a colorless and transparent plate-like molded product was obtained. This molded body was cut into a size of 9 mm ⁇ 9 mm to produce a plastic lid material for a solid-state imaging device package of the present invention, and the evaluation was performed in the same manner as in Example 1. Table 1 shows the results.
  • reaction product solution After cooling the obtained reaction product solution to room temperature, 5 parts of glycidyl methacrylate [component (C)] and tert-butyl peroxy-2-ethylhexanoethyl as a polymerization initiator were added to the reaction product solution. By adding 0.8 parts, A polymerizable solution was prepared.
  • a cavity was formed in the same manner as in Example 3 except that a pair of mold plates were arranged at 1.3 mm intervals, and the prepared radically polymerizable solution was injected into the cavity, and The radical polymerizable solution is polymerized by heating sequentially at different temperatures: 0 hours, 85 hours for 4 hours, 110 ° C. for 1 hour, and 130 ° C. for 1 hour.
  • a colorless and transparent plate-like molded product having a thickness of 1.2 mm made of the crosslinked copolymer was obtained.
  • This molded body was cut into a size of 9 mm ⁇ 9 mm to produce a plastic lid material for a solid-state imaging device package of the present invention, and the evaluation was performed in the same manner as in Example 1.
  • Table 1 shows the results.
  • reaction product solution After cooling the obtained reaction product solution to room temperature, 5 parts of glycidyl methacrylate [component (C)] and te 1-t -butyl propyloxy as a polymerization initiator were added to the reaction product solution.
  • a radically polymerizable solution was prepared by adding 0.8 parts of 2-ethylhexanoet.
  • Example 3 was repeated except that a pair of mold plates was arranged at 0.9 mm intervals.
  • the prepared radically polymerizable solution is injected into the cavity, and the solution is poured at 68 ° C for 10 hours, at 85 ° C for 4 hours, at 110 ° C for 1 hour, and at 130 ° C. so
  • a radical polymerizable solution is prepared by adding 0.8 parts of tert-butyl benzopivalate as a polymerization initiator to the reaction product solution. did.
  • the prepared radically polymerizable solution was poured into a cavity formed in the same manner as in Example 1, and the mixture was poured at 40 ° C for 10 hours, at 65 ° C for 4 hours, and at 80 ° C for 1 hour.
  • the radical polymerizable solution was subjected to a polymerization treatment by sequentially heating at 100 ° C. for 1 hour at a temperature different from that for 1 hour, and a colorless and transparent plate-like molded article having a thickness of 0.9 mm was obtained. .
  • the molded body was cut into a size of 9 mm ⁇ 9 mm to produce a plastic lid material, which was evaluated in the same manner as in Example 1.
  • Table 2 shows the results
  • Example 3 To the resulting mixture was added 1.0 part of tert-butyloxy-111-ethylhexanoetrate, and the mixture was poured into a cavity formed in the same manner as in Example 3; The polymer was heated at 10 ° C for 10 hours, at 65 ° C for 4 hours, at 90 ° C for 1 hour, and at 120 ° C for 1 hour. The monomer melted and leaked, and a molded article could not be obtained.
  • Example 2 The molded body was cut into a size of 9 mm ⁇ 9 mm to produce a plastic lid material, which was evaluated in the same manner as in Example 1. The results are shown in Table 2, and Comparative Example 5> A glass lid material having a thickness of 1 mm was prepared, and items other than heat resistance and bending strength were evaluated in the same manner as in Example 1. Table 2 shows the results.
  • a rid material made of a polycarbonate resin having a thickness of 1 mm was prepared, and items other than heat resistance were evaluated in the same manner as in Example 1. Table 2 shows the results.
  • a lead material made of polymethyl methacrylate resin having a thickness of 1 mm was prepared, and evaluated in the same manner as in Example 1. Table 2 shows the results.
  • Vicat softening "*" Powerful indicates ran at 150 ° C.
  • the lit materials according to Examples 1 to 6 have the same transparency, a lower specific gravity, and a lower cutting density than the glass lit material. It was confirmed that it was excellent.
  • a lid material made of polycarbonate and a lid material made of poly (methyl methacrylate) it has a higher flexural modulus, and is excellent in cutting workability and adhesive toughness. It was confirmed that it was very excellent in solvent resistance.
  • Example 2 In the same manner as in Example 1, a transparent plate-like molded product having a thickness of 0.9 mm made of the acrylic cross-linked copolymer was obtained, and this molded product was cut into a size of 9 mm ⁇ 9 mm. after, by depositing silicon dioxide (S i 0 2) on the surface of its thickness 0. 5 m, pitch 0. 0 5 mm diffraction grating layer having a trapezoidal linear diffraction grating pattern of form The manufactured lid material was manufactured.
  • silicon dioxide Si 0 2
  • a plate-like molded body of an acrylic cross-linked copolymer having dimensions of 80 mm ⁇ 80 mm and a thickness of 1 mm obtained in the same manner as in Example 1 was used as a substrate, and this was placed in a vacuum evaporation apparatus. by an electron beam evaporation method and instrumentation wearing, by depositing silicon dioxide (S i 0 2) and titanium oxide (T i 0 2) alternately on the surface of the substrate, the thin film layer number 4 0 total An optical multilayer film having a thickness of 5 m was formed.
  • Fig. 1 shows the measurement results of the spectral transmission characteristics of this rod material.
  • a peel test using an adhesive tape was performed using the lid material on which the optical multilayer film was formed as a sample, but no separation of the optical multilayer film from the substrate was observed.
  • the lid material was left for 100 hours at a temperature of 6 Ot; and a high temperature and relative humidity of 90% for 100 hours, and then a similar separation test was performed. No separation of the optical multilayer film was observed at all.
  • the plastic lid material according to the present invention has a low specific gravity, is excellent in moldability, and has excellent transparency, adhesive toughness, heat resistance, and solvent resistance, and is used for a solid-state imaging device package. It has sufficiently high strength as a lid material.
  • an acrylic cross-linked copolymer having a diffraction grating formed on its surface having an optical one-pass filter function is formed. Since the body can be obtained directly, a lid material on which a diffraction grating having an optical low-pass filter function is formed can be advantageously produced.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Matériau plastique qui permet de fermer le boîtier d'un élément de prise de vues à semi-conducteur, de faible densité, très facile à fabriquer, transparent, présentant une bonne adhésivité, stable du point de vue dimensionnel, résistant aux solvants et à la chaleur, et ayant d'excellentes caractéristiques mécaniques. Le matériau comprend un copolymère acrylique réticulé préparé par uréthanisation et polymérisation radiculaire entre (A) un monomère d'ester (méth)acrylique comportant un groupe hydroxyle secondaire; (B) au moins un composé di-isocyanate choisi entre le dicyclohexylméthane 4,4'-di-isocyanate, le di-isocyanate d'isophorone et le 1,3-bis-isocyanatométhyl)cyclohexane; et (C) un monomère pouvant subir une copolymérisation radicalaire avec le monomère (A).
PCT/JP1997/004021 1996-11-05 1997-11-05 Materiau plastique pour fermer un boitier d'element de prise de vue a semi-conducteur, et procede de fabrication associe WO1998020560A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8/292283 1996-11-05
JP29228396 1996-11-05

Publications (1)

Publication Number Publication Date
WO1998020560A1 true WO1998020560A1 (fr) 1998-05-14

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PCT/JP1997/004021 WO1998020560A1 (fr) 1996-11-05 1997-11-05 Materiau plastique pour fermer un boitier d'element de prise de vue a semi-conducteur, et procede de fabrication associe

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Country Link
WO (1) WO1998020560A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03215512A (ja) * 1990-01-19 1991-09-20 Mitsubishi Rayon Co Ltd 注型重合用樹脂組成物
JPH04282991A (ja) * 1991-03-12 1992-10-08 Hitachi Ltd 固体撮像装置
JPH05313099A (ja) * 1992-05-11 1993-11-26 Mitsui Petrochem Ind Ltd 回折格子型光学的ローパスフィルタ、パッケージ部材および固体撮像素子
JPH06112460A (ja) * 1992-09-25 1994-04-22 Sony Corp 固体撮像装置
JPH06128502A (ja) * 1992-10-16 1994-05-10 Mitsubishi Rayon Co Ltd 被覆材組成物
JPH0732381A (ja) * 1993-07-20 1995-02-03 Canon Inc 複合型精密成形品の製造方法およびその成形型
JPH08181298A (ja) * 1995-07-27 1996-07-12 Olympus Optical Co Ltd 固体撮像装置
JPH09102620A (ja) * 1995-10-03 1997-04-15 Kureha Chem Ind Co Ltd 半導体素子パッケージ用プラスチック製リッド材およびその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03215512A (ja) * 1990-01-19 1991-09-20 Mitsubishi Rayon Co Ltd 注型重合用樹脂組成物
JPH04282991A (ja) * 1991-03-12 1992-10-08 Hitachi Ltd 固体撮像装置
JPH05313099A (ja) * 1992-05-11 1993-11-26 Mitsui Petrochem Ind Ltd 回折格子型光学的ローパスフィルタ、パッケージ部材および固体撮像素子
JPH06112460A (ja) * 1992-09-25 1994-04-22 Sony Corp 固体撮像装置
JPH06128502A (ja) * 1992-10-16 1994-05-10 Mitsubishi Rayon Co Ltd 被覆材組成物
JPH0732381A (ja) * 1993-07-20 1995-02-03 Canon Inc 複合型精密成形品の製造方法およびその成形型
JPH08181298A (ja) * 1995-07-27 1996-07-12 Olympus Optical Co Ltd 固体撮像装置
JPH09102620A (ja) * 1995-10-03 1997-04-15 Kureha Chem Ind Co Ltd 半導体素子パッケージ用プラスチック製リッド材およびその製造方法

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