JP2002201264A - Composition for sealing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for a resin suitable for encapsulation of a semiconductor or a liquid crystal panel which is excellent in various physical properties which is cured by a small amount of active energy ray irradiation or a short heat treatment. . SOLUTION: The composition containing a compound having at least one oxetanyl group and at least one epoxy group in the same molecule has a small amount of active energy ray irradiation, low temperature, short time curing, and various physical properties. It has been found that they exhibit excellent sealing properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition used for sealing electronic parts such as semiconductors and liquid crystal panels.
The present invention also relates to a cured product produced using the composition and an apparatus using the same. More specifically, it is characterized by containing a compound having at least one oxetanyl group and at least one epoxy group in the same molecule, and is characterized by a small amount of active energy ray irradiation, low temperature, and high productivity which cures in a short time. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Semiconductor electronic components such as diodes, transistors and ICs are sealed with a ceramic package or a resin package in order to mechanically and chemically protect them from an external environment. In recent years, flip-chip mounting, in which a bare chip is directly connected to a printed circuit board, has attracted attention as a semiconductor chip mounting method. In this method, the metal bump electrode on the element forming surface of the bare chip is melt-connected to the electrode pad formed on the printed circuit board, and an underfill agent is used between the circuit board and the chip to reduce stress. A sealant is used.

A liquid crystal display has a structure in which a liquid crystal is sealed between two parallel liquid crystal substrates and a transparent electrode is laminated on the liquid crystal substrate. As a sealing material for sealing the liquid crystal, A sealant is used. This conventional sealant uses an epoxy resin as the main component and a phenol resin or an amine-based or acid-anhydride-based curing agent as a curing agent, requires high-temperature treatment at about 170 ° C, and has storage stability. It was bad and required storage at a low temperature, and in the case of a liquid resin composition, it was necessary to separate the main agent and the curing agent and store them as two liquids. Japanese Patent Application Laid-Open No. 11-17074 discloses a sealant using cationic polymerization. The curing speed of an oxetane compound alone or a mixture of an oxetane compound and bisphenol A diglycidyl ether is higher than that of bisphenol A diglycidyl ether. But the curability at low temperatures is still insufficient.

[0004] Apart from these heat-curing methods, ultraviolet-curable sealant compositions have been studied for the purpose of improving productivity and sealing heat-sensitive devices. JP-A-11-1
Japanese Patent Publication No. 99651 points out problems such as poor moisture resistance and poor adhesion when a vinyl ester such as a radical-curable epoxy acrylate or urethane acrylate is used as the ultraviolet-curable sealant composition. . JP-A-59-54277 discloses that when a cationically polymerizable sealant composition comprising an epoxy resin and an allylonium salt is used, since the curing shrinkage is smaller than that of a radical-curable type, no crack is formed during sealing. And that no internal stress remains. Also, Japanese Patent Application Laid-Open No. 2000-1
Japanese Patent No. 91751 discloses an ultraviolet-curable resin composition using an epoxy compound and tetrakis (pentafluorophenyl) borate as a counter anion as an initiator, but both require large irradiation energy for curing and further improve productivity. Has been desired.

US Pat. No. 3,388,105 discloses that a compound having an oxetanyl group and an epoxy group in the same molecule is cured by a heat addition reaction with a compound having a carboxyl group, and the alicyclic alkane is cationically ring-opened. It is not known that it shows extremely high activity (curability) against polymerization, and the composition of a sealing resin composition excellent in various physical properties that is cured by a small amount of active energy ray irradiation or a short heat treatment. It was not known at all that it was particularly suitable as a component.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is a composition for a sealing resin excellent in various physical properties which is cured by a small amount of active energy ray irradiation or a short heat treatment. Specifically, the present invention provides a resin composition suitable for encapsulating semiconductors such as diodes, transistors, and ICs, encapsulating photoelectric elements and light-emitting elements, underfilling materials for flip-chip mounting, and encapsulants for liquid crystal panels. That is the task.

[0007]

Means for Solving the Problems As a result of intensive studies on the solution of the above problems, the present inventors have identified a compound containing a compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule. It has been found that the problem can be solved by the resin composition of the present invention, and the present invention has been completed.

That is, the present invention provides the following [1] to [1]
6], a cured product thereof, and a sealed device. [1] A composition for a sealing resin, comprising a compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule. [2] The composition for a sealing resin according to [1], wherein the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule is an alicyclic alkane. [3] The sealing according to [2], wherein the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule includes a compound represented by the general formula (1). A composition for a resin stopper.

Embedded image Wherein R is a hydrogen atom or a methyl group, and m is 0 to 2
N is 2 when m is 0, and 1 otherwise.) [4] As a compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule, 7,8-epoxy-2-oxa-5-methyl-spiro [3.5] nonane and / or 6,7-epoxy-
The composition for a sealing resin according to [3], further comprising 2-oxa-spiro [3.5] nonane. [5] Including a compound (b) that initiates cationic polymerization by irradiation with active energy rays and / or heating [1]
The composition for a sealing resin according to any one of [1] to [4]. [6] The encapsulation according to [5], wherein the compound (b) that initiates cationic polymerization by irradiation with active energy rays and / or heating is at least one selected from a sulfonium salt, an iodonium salt and a diazonium salt. Composition for resin. [7] The composition for a sealing resin according to any one of [1] to [6], which contains a compound (c) having one or more epoxy groups and not having an oxetanyl group. [8] The sealing resin composition according to any one of [1] to [7], which contains a compound (d) having one or more oxetanyl groups and not having an epoxy group. [9] The composition for a sealing resin according to any one of [1] to [8], containing the compound (e) having a radical polymerizable unsaturated group. [10] containing a photo-radical polymerization initiator (f) [1]
The composition for a sealing resin according to any one of [9] to [9]. [11] The composition for a semiconductor sealing resin [1] to [1]
0]. The composition for a sealing resin according to any one of the above. [12] A composition for a liquid crystal panel sealing resin [1] to
The composition for a sealing resin according to any one of [10]. [13] A cured product obtained by curing the sealing resin composition according to any one of [1] to [12]. [14] The composition for a sealing resin is cured by irradiation with active energy rays and / or heating.
3] The method for producing a cured product according to the above. [15] The method for producing a cured product according to [14], wherein the active energy rays are ultraviolet rays. [16] An apparatus sealed with a cured product of the composition according to any one of [11] to [13].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule used in the present invention includes, for example, an alicyclic ring having at least one oxetanyl group and at least one epoxy group in the same molecule. Formula alkanes are mentioned. Examples include the following. That is, 3-ethyl-3-[(oxiranylmethoxy) methyl] oxetane, 7,8-epoxy-2-oxa-5-methyl-spiro [3.5] nonane, 6,7-epoxy-2-oxa −
Spiro [3.5] nonane, spiro [5,6-epoxynorbornane-2,3′-oxetane], spiro [5,6
-Epoxy-3-methylnorbornane-2,3'-oxetane] and the like. Furthermore, 7,8-epoxy-2-oxa-5-methyl-spiro [3.6] decane, 5,6-
Epoxy-2-oxa-spiro [3.6] decane is also included. Among these, 7,8-epoxy-2-oxa-5-methyl-spiro [3.5] nonane and 6,7-epoxy-2-oxa-spiro [3.5] nonane are preferred.

The compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule can be easily synthesized by a known method,
For example, a synthesis method is described in U.S. Pat. No. 3,388,105.

The compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule can be used alone or as a mixture of two or more. A cured product formed from a resin composition containing a compound having an oxetanyl group in the molecule has good water resistance as a result since it has low water absorption. Further, since the degree of shrinkage upon curing is small, the cured product has a feature of being excellent in dimensional stability.

In the present invention, the compound (b) which initiates cationic polymerization by irradiation with active energy rays and / or heating is changed by heating or irradiation with active energy rays such as ultraviolet rays to initiate cationic polymerization such as acid. It can be a compound that produces a substance. Therefore, compound (b) is a kind of cationic polymerization initiator, and is also referred to in the art as "acid generator". Hereinafter, in the present invention, the compound (b) is referred to as an acid-generating cationic polymerization initiator.

The acid-generating cationic polymerization initiator is capable of opening both groups of the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule of the present invention by heating or irradiation with light such as ultraviolet rays. It is blended in order to promote the ring cationic polymerization and smoothly promote the curing of the formed cured product or coating film.

The acid-generating cationic polymerization initiator referred to in the present invention is a compound that changes upon heating or irradiation with active energy rays such as ultraviolet rays to generate a substance that initiates cationic polymerization such as an acid. Thus, compounds which are in the acid form from the beginning are not included.

As the acid-generating cationic polymerization initiator, known sulfonium salts, iodonium salts, phosphonium salts,
Examples thereof include diazonium salts, ammonium salts, and ferrocenes. Specific examples are shown below, but the present invention is not limited to these compounds.

As the sulfonium salt-based acid-generating cationic polymerization initiator, bis [4- (diphenylsulfonio)
Phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfo) Nio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetra Fluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, tri Phenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfo) Nio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4
-(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfidetetrakis ( Pentafluorophenyl) borate, and the like.

Examples of the iodonium salt-based cationic polymerization initiator include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and bis (dodecylphenyl). ) Iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1 −
Methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4
-Methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl)
Borate, and the like.

Examples of the diazonium salt-based cationic polymerization initiator include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate. .

Examples of the ammonium salt type acid-generating cationic polymerization initiator include 1-benzyl-2-cyanopyridinium hexafluorophosphate and 1-benzyl-2-phosphate.
Cyanopyridinium hexafluoroantimonate,
1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1-
(Naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-
Cyanopyridinium hexafluoroantimonate,
1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-
Cyanopyridinium tetrakis (pentafluorophenyl) borate; and the like.

Examples of the ferrocene-based cationic polymerization initiator include (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate and (2,4 -Cyclopentadien-1-yl) [(1-methylethyl) benzene]-
Fe (II) hexafluoroantimonate, 2,4-cyclopentadien-1-yl) [(1-methylethyl)
Benzene] -Fe (II) tetrafluoroborate, 2,
4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate, and the like.

Among these acid-generating cationic polymerization initiators, sulfonium salt and iodonium salt-based initiators are preferred from the viewpoints of curing speed, stability and economy. Commercial products include Asahi Denka Kogyo's SP-150, SP-170, CP
-66, CP-77; CYRA manufactured by Union Carbide
CURE-UVI-6990, UVI-6974; CI-2855, CI-2639, manufactured by Nippon Soda Co., Ltd .; San-Aid SI-60, manufactured by Sanshin Chemical Industries; "Irgacure 261"
((2,4-cyclopentadien-1-yl) [(1-methylethyl) manufactured by Ciba Specialty Chemicals)
Benzene] -Fe (II) hexafluorophosphate), "RHODORSIL 207
4 "; (4-methylphenyl-4 manufactured by Rhone Poulin Co.)
-(1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate) and the like.

These acid-generating cationic polymerization initiators are selected from the above-mentioned materials, and can be used alone or in combination of two or more.
The preferred range of the amount of the acid-generating cationic polymerization initiator used is
Although there is no particular limitation, the compounding amount of the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule (when a compound capable of cationic polymerization such as a compound having an epoxy group described below is used in combination, 0.05-25 parts by mass with respect to 100 parts by mass of the total amount thereof)
Preferably it is 1 to 20 parts by mass. If the addition amount is less than 0.05 parts by mass, sensitivity becomes poor and curing is required, so that extremely large light irradiation energy and prolonged high-temperature treatment are required. Further, even if it is added in excess of 25 parts by mass, the sensitivity is not improved, which is not economically preferable. Conversely, the amount remaining as an uncured component in the film increases, and the cured physical properties may be reduced.

As the compound (c) having one or more epoxy groups in the molecule of the present invention and not having an oxetanyl group, known and commonly used epoxy compounds can be used. When an epoxy compound is added to the composition for a sealing resin of the present invention, the heat resistance and chemical resistance of the obtained cured film are further improved. This epoxy compound is not particularly limited as long as it has one or more epoxy groups in one molecule.

Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,
Bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolak epoxy resin (for example, phenol novolak epoxy resin, cresol novolak epoxy resin, Brominated phenol novolak type epoxy resin), hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether,
Triglycidyl isocyanurate and the like can be used.

Further, as the aliphatic epoxy compound,
(3,4-epoxycyclohexyl) methyl-3 ′,
4'-epoxycyclohexylcarboxylate, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-
6-methylcyclohexylmethyl) adipate, 3,4
-Epoxy-6-methylcyclohexyl-3 ', 4'-
Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexane) Carboxylate).

Further, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
1 for aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol, and glycerin
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides; diglycidyl ethers of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; butyl glycidyl ether; Phenyl glycidyl ether, cresol glycidyl ether, nonylphenyl glycidyl ether, glycidyl methacrylate;
Phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohol obtained by adding alkylene oxide thereto; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxystearate, octyl epoxystearate, epoxidized ani Oil, epoxidized polybutadiene and the like can be mentioned.

The compounds (c) having one or more epoxy groups in the molecule and no oxetanyl group can be used alone or as a mixture of two or more. The compounding amount of the compound (c) (the total amount when two or more kinds are used in combination) is 100 parts by mass of the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule in the present invention. 1 to 10,000
Parts by mass are preferred, and 10 to 1,000 parts by mass are particularly preferred.

The encapsulating resin composition of the present invention has a molecular weight within a range not to impair the object of the present invention in order to adjust the viscosity of the whole composition, to improve water resistance and to reduce curing shrinkage. Compound (d) having one or more oxetanyl groups and no epoxy group can be added.

Specific examples of compound (d) include trimethylene oxide, 3,3-dimethyloxetane,
Dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd .; trade name: EOXA), bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Benzene (alias xylylene oxetane; manufactured by Toagosei Co., Ltd .; trade name XDO), tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis [(3-ethyl-3-oxetanylmethoxy) methylphenyl] ether, (3-ethyl-3-oxetanylmethoxy) oligodimethylsiloxane or a compound having a high molecular weight polyvalent oxetane ring, specifically, an oxetane oligomer (manufactured by Toagosei Co., Ltd .; trade name: Oligo-OXT), 2-oxaspiro [3 .5] nonane, 7-methyl-2-oxaspiro [3.5] nonane, spiro [adamantane-2,3 ′
-Oxetane], spiro [bicyclo [2.2.1] heptane-2,3'-oxetane], spiro [bicyclo [2.2.2] octane-2,3'-oxetane], spiro [7-oxabicyclo [2.2.1] Heptane-
2,3'-oxetane], 2-oxaspiro [3.5]
Nona-6-ene, 5-methyl-2-oxaspiro [3.
5] Nona-6-ene, spiro [bicyclo [2.2.1]
Hept-5-ene-2,3'-oxetane], spiro [3-methylbicyclo [2.2.1] hept-5-ene-2,3'-oxetane], 5-methyl-2-oxaspiro [3 .5] nonane, spiro [3-methylbicyclo [2.2.1] heptane-2,3′-oxetane] and the like. These compounds (d) can be used alone or
It can be used as a mixture of more than one species.

The compounding amount of the compound (d) (the total amount when two or more kinds are used in combination) is the compound (a) of the present invention having at least one oxetanyl group and at least one epoxy group in the same molecule. 1 to 100 parts by mass
It is 10,000 parts by mass, preferably 10 to 1,000 parts by mass. When a compound having only one cationically polymerizable group in the molecule among the above-mentioned presenting compound (d) is added in an amount of 200 parts by mass or more based on 100 parts by mass of the alicyclic alkane (a), dryness to the touch becomes poor. Further, the heat resistance and PCT (pressure cooker test) resistance of the obtained cured product are undesirably reduced.

In the present invention, the following cationically polymerizable monomers can also be added to the sealing resin composition. The cationically polymerizable monomer is a compound that causes a polymerization initiation reaction or a cross-linking reaction by the acid generated by the acid-generating type cationic polymerization initiator, and is classified into compounds other than (a), (c), and (d). For example, tetrahydrofuran,
Oxolane compounds such as 2,3-dimethyltetrahydrofuran; trioxane, 1,3-dioxolane,
Cyclic acetal compounds such as 6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; thiirane compounds such as ethylene sulfide, 1,2-propylene sulfide and thioepichlorohydrin; Thietane compounds such as dimethyl thiethane; vinyl ether compounds such as ethylene glycol divinyl ether, triethylene glycol divinyl ether, and trimethylolpropane trivinyl ether; spiro ortho ester compounds which are reaction products of epoxy compounds and lactones; vinyl cyclohexane, isobutylene, Ethylenically unsaturated compounds such as polybutadiene; cyclic ether compounds; cyclic thioether compounds; vinyl compounds and the like.

These cationically polymerizable monomers can be used alone or in combination of two or more.

The compound (e) having a radically polymerizable unsaturated group is added to the encapsulating resin composition of the present invention within a range not to impair the object of the present invention in order to improve photocurable (active energy ray) curability. It is also possible to add. Compound (e)
Although there is no particular limitation, a (meth) acrylate-based known and commonly used radically polymerizable monomer can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol mono (meth) acrylate, etc. Functional (meth) acrylate compound; ethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyfunctional epoxy (meth) acrylate resin, polyfunctional urethane (meth) acrylate Resins and the like can be mentioned.

The amount of the compound (e) to be added is 5 to 200 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of the total of the cationically polymerizable compounds (a), (c) and (d). . If the addition amount exceeds 200 parts by mass, the dryness to the touch becomes poor. Further, since the ratio of crosslinking of the (meth) acrylic group increases in the formation of the film, the heat resistance and PCT resistance of the obtained cured film decrease.

As the photo-radical initiator (f) for smoothly promoting the radical polymerization of the above-mentioned compound having a radical-polymerizable unsaturated group, known photo-radical initiators which generate radicals in response to light can be used. Here, “light” means radiation such as visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. Examples of the photoradical initiator (f) include benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-
ON (manufactured by Ciba Specialty Chemicals; Irgacure 907), 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichloro Benzophenone, 2-methylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, p-dimethylaminebenzoic Acid ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF; Lucilin TP)
O), bis (2,6-dimethoxybenzoyl) -2,
4,4-trimethyl-pentylphosphine oxide-containing initiator (manufactured by Ciba Specialty Chemicals; Irgacure 1700, 149, 1800), bis (2,
4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals);
Irgacure 819). These can be used alone or as a mixture of two or more.

The amount of the photo-radical initiator (f) used depends on the amount of the compound (e) having a radical polymerizable unsaturated group in the composition.
And, if necessary, an alkali-soluble resin (g) to be described below, which is 0.007 to 0 .0 to 1 equivalent of the total (meth) acrylic group equivalent of the (meth) acrylic group-containing resin.
It is 5 mol, preferably 0.035 to 0.3 mol. If the amount of the photo-radical initiator is less than 0.007 mol, the sensitivity becomes poor. On the other hand, if it exceeds 0.5 mol, the sensitivity is not improved, which is not economically preferable.

The composition for a sealing resin of the present invention may further contain an ion exchanger for the purpose of removing an acid component present after curing. Examples of such an ion exchanger include Amberlite CG120 (manufactured by Organo), Tomix AD500,
600 (manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward 500, 600
(Manufactured by Kyowa Chemical), IXE-500, 600, 633,
700, 1100, 1320 (manufactured by Toa Gosei Chemical Co., Ltd.), and the like. This ion exchanger may be used in an amount of 2 to 12 parts by mass, preferably about 4 to 8 parts by mass, per 1 part by mass of the acid generating type cationic polymerization initiator. This ion exchanger suppresses corrosion of the aluminum deposition surface of the disk, the chip of the IC card, and the oscillation coil due to the acid component remaining after curing.

The composition for a sealing resin of the present invention is usually used without a solvent, but a solvent may be added as a viscosity modifier for adapting to the method of use. Specifically, ethylene glycol monoalkyl ether or its acetates; diethylene glycol mono or dialkyl ethers; propylene glycol monoalkyl ether or its acetates; dipropylene glycol mono or dialkyl ethers; methyl carbitol, butyl carbitol, butyl cellosolve Known organic solvents such as acetate, carbitol acetate, ethyl methyl ketone, cyclohexane, toluene, xylene, tetramethylbenzene, petroleum ether, petroleum naphtha, solvent naphtha; or additives known in the art such as plasticizers , Solvents and the like, and these can be used alone or in combination of two or more.

The amount of these solvents to be added is 0 to 2000 parts by mass based on 100 parts by mass of the compound (a) of the present invention having at least one oxetanyl group and at least one epoxy group in the same molecule. It can be selected appropriately according to the method.

Further, a release agent may be added to the composition for a sealing resin of the present invention in order to give a good release property from a mold at the time of molding. As the release agent, oxidized or non-oxidized polyolefin (for example, H4 or P4 manufactured by Hoechst)
E, average molecular weight of PED series etc. is 500-1000
0 low molecular weight polyethylene), natural wax, synthetic wax, montanic acid ester, montanic acid, stearic acid, higher fatty acids and metal salts thereof, paraffin, etc., and these may be used alone or in combination of two or more. Can be. It is preferable to add 0.01 to 10 parts by mass, preferably 0.1 to less than 5.0 parts by mass, based on 100 parts by mass of the total sealing composition. If the amount is less than 0.01 part by mass, sufficient releasability cannot be obtained, and if it exceeds 10 parts by mass, the adhesiveness may be impaired.

The composition for a sealing resin of the present invention may contain an inorganic filler for the purpose of improving properties such as heat resistance, adhesion and hardness. Specifically, powders of fused silica powder, crystalline silica powder, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllium, zirconia, talc, clay, aluminum hydroxide, etc., Alternatively, one or more kinds of spherical beads, potassium titanate, silicon carbide, silicon nitride, single crystal fiber such as alumina, glass fiber, and the like can be used. Among these inorganic fillers, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. The amount used is preferably from 0 to 2,000 parts by mass based on 100 parts by mass of the total composition for sealing resin. It is preferable that the inorganic filler is sufficiently mixed in advance.

When the composition for a sealing resin of the present invention is polymerized by ultraviolet rays, which is one of the active energy rays, a sensitizer may be used in order to improve the polymerization rate.
Examples of the sensitizer used for such a purpose include pyrene, perylene, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, and phenothiazine. When the sensitizer is used in combination, the amount of the sensitizer used is 10
The range of 0.1 to 100 parts by mass relative to 0 parts by mass is preferred.

If necessary, known and conventional coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black; silicone-based, fluorine-based, and polymer -Based antifoaming agents; leveling agents; adhesion-imparting agents such as imidazole-based, thiazole-based, triazole-based, and silane coupling agents; antimony trioxide, phosphate esters, red phosphorus, and nitrogen-containing compounds including melamine resins And other known additives such as a flame retardant such as silicone oil and silicone rubber powder, a stress relieving agent such as silicone oil and silicone rubber powder, and an ion trapping agent such as hydrotalcite and antimony-bismuth.

The composition for a sealing resin of the present invention can be obtained by mixing constituent materials such as the compounds (a) and (b) described above with a known and commonly used mixing apparatus. The mixing device is not particularly limited as long as it can uniformly mix the respective constituent substances, but it is necessary to select the mixing device in consideration of the viscosity of the composition and the like.

The composition for a sealing resin in the present invention can be polymerized (cured) by irradiation with active energy rays and / or heating. The term “active energy ray” as used herein refers to ultraviolet rays, X-rays, electron beams, γ-rays, and the like. When irradiating ultraviolet rays, the light sources include metal halide lamps, mercury arc lamps, xenon arc lamps, fluorescent lamps,
Carbon arc lamps, tungsten-halogen copy lamps, sunlight, and the like.

The irradiation conditions for the sealant are usually about 10
１，1,000 mJ / cm ² , preferably about 10-500
mJ / cm ² , more preferably about 10-100 mJ / c
m ² is suitable. When using heating,
Curing is from room temperature (about 25 ° C) to 250 ° C, preferably about 50 ° C.
The reaction may be carried out at a temperature of about 200 to 200C, more preferably about 75 to 150C for about 1 to 60 minutes, preferably about 5 to 30 minutes, more preferably about 10 to 20 minutes.

Examples of the device sealed with the sealing resin composition of the present invention include a semiconductor element and a liquid crystal panel. The semiconductor sealing device manufactured by the present invention can be easily manufactured by sealing a semiconductor element (chip) using the above-described composition for a sealing resin. As semiconductor elements for sealing, for example, in addition to light source, detection, passive and other opto devices, integrated circuits, large-scale integrated circuits,
Elements such as a transistor, a thyristor, and a diode are included. In addition, an underfill sealant for flip-chip mounting is also exemplified and is not particularly limited.

The most common sealing method is a low pressure transfer molding method, but sealing by injection molding, compression molding, casting or the like is also possible. After sealing with a sealant composition,
Cured by irradiation of active energy rays or heating,
Finally, a semiconductor sealing device sealed with the cured product is obtained.

The case of curing by irradiation with active energy rays will be described in more detail. For example, the composition is placed in a mold made of a material through which active energy rays can easily pass, such as glass, ceramic, plastic, and silicone rubber, and the semiconductor element is immersed. Then, a method of irradiating active energy rays as they are and hardening, and then removing the mold is adopted. For sealing the light emitting diode, for example, a bell shape, a lens shape, or the like is used as the shape of the mold.

In sealing a liquid crystal panel, the composition for a sealing resin of the present invention is applied using a dispenser or the like, leaving one opening on the outer periphery of the flat surface of the glass substrate. A glass substrate of the same size as
The liquid crystal panel can be obtained by superposing the sealing material layers so as to be between the glass substrates, irradiating with an active energy ray and curing the liquid crystal, injecting a liquid crystal from an opening, and closing the opening.

[0051]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The “parts” in Examples and Comparative Examples
Represents parts by mass unless otherwise specified.

Among the materials used in Examples and Comparative Examples, commercially available products are as follows, and were used without purification.

XDO: 1,4-bis [(3
-Ethyl-3-oxetanylmethoxy) methyl] benzene KRM-2110: manufactured by Asahi Denka Kogyo Co., Ltd., alicyclic epoxy-based resin UVI-6990: manufactured by Union Carbide, photocationic polymerization initiator EOCN-1020: manufactured by Nippon Kayaku , O-cresol novolak type epoxy resin Epicoat 828: Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin San Aid SI-100L: Sanshin Chemical Industry Co., Ltd., cationic polymerization initiator M-309: Toagosei Co., Ltd., trimethylol Propane triacrylate Irgacure 907: Ciba Specialty Chemicals, photopolymerization initiator As the inorganic filler, commercially available spherical fused silica having an average particle size of 5 μm was used.

The compounds not commercially available used were those chemically synthesized by the inventors. 7,8-Epoxy-2-oxa-5-methylspiro [3.5] nonane and 6,7-epoxy-2-oxaspiro [3.5] nonane are described with reference to the method described in U.S. Pat. No. 3,388,105. Was synthesized. Specifically, 7,8-epoxy-2-oxa-5-methyl-spiro [3.5] nonane was synthesized as follows.

<Synthesis of 7,8-epoxy-2-oxa-5-methyl-spiro [3.5] nonane> 1) Synthesis of 2-methyl-4-cyclohexene-1,1-dimethanol Three-necked flask Of butadiene and crotonaldehyde
327 g of 2-methyl-4-cyclohexene-1-carbaldehyde, which is a Diels-Alder reaction product, 600 ml of methanol and 729 g of 37% formalin water were added thereto, and the solution was heated to 60 ° C. while stirring. Subsequently, a solution in which 252 g of KOH was dissolved in 600 ml of distilled water was added dropwise over 2 hours. After stirring was continued for 7 hours, the reaction solution was concentrated under reduced pressure to obtain a two-layer residue. The oil layer concentrated to about 150 ml was washed with 300 ml of distilled water. After concentrating the oil layer under reduced pressure, 50 mg of 3,5-di (t-butyl) -4-hydroxytoluene (BHT) was added, and the mixture was distilled under reduced pressure to obtain 2-methyl-4-cyclohexene-1,1, a colorless crystal. 311 g of dimethanol (82% yield) were obtained.

2) 2-Methyl-4-cyclohexene-
Synthesis of 1,1-dimethanol cyclic carbonate 2-methyl-4-cyclohexene-
310 g (1.99 mol) of 1,1-dimethanol, 894 g of dimethyl carbonate (DMC) and 0.9 g of potassium carbonate
3 g was charged, the temperature was raised to 90 ° C., and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature, and potassium carbonate was separated by filtration. After adding 120 mg of BHT, the remaining DMC and methanol were removed under reduced pressure of 2 kPa (15 mmHg), followed by distillation under reduced pressure to obtain 2-methyl-4-cyclohexene-1,1-dimethanol cyclic which was colorless crystals at room temperature. 32 carbonates
6 mg (89.4% yield) was obtained.

3) 2-oxa-5-methylspiro [3.
5] Synthesis of Nona-7-ene 3-Methyl-4-cyclohexene-
321.15 g of 1,1-dimethanol cyclic carbonate, BH
642 mg (0.2% by mass) of T and 1.93 g of LiCl were charged, and heated and stirred at 275 ° C. using a mantle heater. The product was immediately taken out of the system under a reduced pressure of about 8 kPa (60 mmHg), and heating was continued for 4 hours until the distillation stopped. BHT (600 mg) was added to the product, and the mixture was distilled under reduced pressure to give a colorless transparent liquid, 2-oxa-5-methylspiro.
[3.5] Nona-7-ene was obtained in an amount of 187 g (yield: 71%).

4) 7,8-epoxy-2-oxa-5-
Synthesis of methyl-spiro [3.5] nonane 50 g of 2-oxa-5-methylspiro [3.5] non-7-ene was dissolved in 150 ml of dichloromethane and charged into the reactor. A suspension of 93.7 g of m-chloroperbenzoic acid in 400 ml of dichloromethane was added dropwise over 1 hour so that the reaction solution did not exceed 40 ° C. The precipitated m-chlorobenzoic acid was separated by filtration and washed well with cold dichloromethane. 15.0 g of calcium hydroxide in the organic layer
Was added and stirred for 30 minutes, and the precipitated crystals were separated by filtration and washed with cold dichloromethane. The organic layer was washed with 5% NaHSO ₄
After washing with water and a saturated saline solution, the mixture was concentrated and distilled under reduced pressure at room temperature to give a colorless semisolid 7,8-epoxy-2-oxa-
38.1 g (yield 73.7%) of 5-methyl-spiro [3.5] nonane was obtained.

6,7-Epoxy-2-oxaspiro [3.5] nonane was also synthesized by the present inventors by a procedure similar to the above. Also, 5-methyl-2-oxaspiro [3.
5] Nonane was synthesized by the present inventors as follows.

<5-Methyl-2-oxaspiro [3.
5] Synthesis of nonane> 2-methyl-
474 g of cyclohexane-1,1-dimethanol, 405 g of dimethyl carbonate, and 1.4 g of potassium carbonate were added, and the mixture was heated and stirred at a temperature of 100 ° C. in an oil bath. Performed for 14 hours.
Finally, the pressure inside the reaction vessel was reduced to 10 mmHg, and the corresponding carbonate ester was obtained in a yield of 95%.

The obtained cyclic carbonate was used as it was in 25
The mixture was heated and stirred at 0 ° C., and the reaction was performed for 10 hours while discharging the generated carbon dioxide gas from the upper part of the cooling device to the outside of the system. This reaction solution was purified by distillation to give 5-methyl-2-oxaspiro [3.
5] 230 g of nonane was obtained. (Example 1) 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane (30 parts by mass), Epikote 828 (65 parts by mass), Sun-Aid SI-100L (5 parts by mass)
Parts by mass) and kneaded using three 5-inch rolls to prepare a viscous liquid sealing resin composition. Height 30
The prepared resin composition was injected into a mold having a size of 15 mm × width 15 mm × depth 5 mm, and after sufficient defoaming, a silicon element for evaluation having aluminum wiring of 9 mm square was immersed. Then, it was left still in an oven at 120 ° C. for 10 minutes. The cured product was sufficiently cured when it was taken out of the oven and returned to room temperature, and a cured product in which the silicon element was sealed was obtained.

Comparative Example 1 7,8-Epoxy-2-oxa-5-methylspiro [3.5] nonane (3
0 parts by mass) and the same operation as described above except that epicoat 828 (65 parts by mass) was changed to epicoat 828 (75 parts by mass), and an attempt was made to seal the silicon element. However, the composition was insufficiently cured and remained liquid.

Comparative Example 2 The 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane (3
The same operation was performed except that XDO (30 parts by mass) was changed from 0 parts by mass to seal the silicon element. However, the curing of the composition was insufficient.

Therefore, the composition for sealing resin according to the present invention (Example 1), which contains the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule, (Example 1) It is clear that the composition cures in a shorter heating time than the composition for a sealing resin containing only an epoxy resin or a compound having only an oxetanyl group as the main component (each of Comparative Examples 1 and 2).

(Examples 2 and 4, Comparative Examples 3 and 4) A composition for a sealing resin was prepared from each component shown in Table 1 in exactly the same manner as in Example 1, and a silicon element was sealed. A test piece was obtained. Curability of the obtained test specimen, heat cycle resistance,
The results of PCT resistance are shown in Table 1. The test after curing was not performed for Comparative Example 3 which was not cured. In addition, each evaluation method was performed as follows.

1) Curability ○ ····· Fully cured inside × × ··· Not fully cured inside 2) Heat cycle resistance Minutes, then at 100 ° C for 1 minute
The test was repeated 10 times with one cycle of standing for 0 minutes, and the state of the test piece was observed. ○ ・ ・ ・ ・ No abnormality △ ・ ・ ・ ・ Some cracks are observed × ・ ・ ・ ・ Cracks are generated entirely 3) Pressure cooker (PCT) resistance Autoclave (MODEL
SS-240), left for 300 hours under a saturation condition of 121 ° C., 2 atm, and 100% relative humidity, taken out, and observed the state of the test piece. ○ ・ ・ ・ ・ No abnormality △ ・ ・ ・ ・ Slight discoloration on the element part × ・ ・ ・ ・ Discoloration occurs on the entire surface and the element is corroded

[0067]

[Table 1]

From the results shown in Table 1, it can be seen that the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule contains a compound (a) for a sealing resin according to the present invention. Examples 2 to 4) are superior in all aspects of curability, heat cycle resistance and PCT resistance to the composition for a sealing resin containing only an epoxy resin as a main component (Comparative Example 3), and have an epoxy resin and an oxetanyl group. It is evident that the compound having only a compound having only PCT is superior to the composition for a sealing resin (Comparative Example 4) in PCT resistance.

Examples 5 to 8 and Comparative Example 5 The components shown in Table 2 were mixed and kneaded in the same manner as in Example 1 to prepare a composition for a sealing resin. Height 30mm x width 15
After the prepared resin composition was poured into a glass mold having a size of 5 mm × 5 mm in depth and sufficiently defoamed, a silicon element for evaluation having a 9 mm square aluminum wiring was immersed. Then, use a metal halide lamp (UVC-302 manufactured by Ushio Inc.)
/ 1 MN: 302 / 5XX-DX01, mounted lamp UV
L-30000M2-N1), 300 mJ / c
Irradiated with m ² active energy rays. After curing, the cured product was released from the glass mold to obtain a test piece in which the silicon element was sealed.

Table 2 shows the results of the curability, heat cycle resistance and PCT resistance of the obtained test pieces.

[0071]

[Table 2]

From the results in Table 2, it is found that the composition for a sealing resin according to the present invention, which contains the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule (embodiment) Examples 5 to 8) were superior in heat resistance under short-time active energy ray irradiation conditions compared to the composition for a sealing resin containing epoxy resin and a compound having only an oxetanyl group as a main component (Comparative Example 5). It is clear that it gives cyclability and PCT resistance.

Example 9 7,8-Epoxy-2-oxa-5-methylspiro [3.5] nonane (30 parts by mass), Epikote 828 (65 parts by mass), Sun-Aid S
I-100L (5 parts by mass), spacer (Sekisui Fine Chemical polymer beads, Micropearl SP-20
7, a primary particle size of 7 μm) and 1.5 parts by mass were sufficiently mixed using a stirrer to prepare a composition for a liquid crystal panel sealing resin. Using a resin dispenser, this resin composition
A line width of 1 mm ± 1 mm, leaving one opening of 2 mm width on the outer periphery of a plane of a 90 mm × 150 mm glass substrate.
It was applied so as to form a sealing material layer having a thickness of 0.05 mm and a thickness of 7.5 μm. A glass substrate having the same size as the applied glass substrate is overlapped so that the sealing material layer is between the glass substrates, and a metal halide lamp (UVC- manufactured by Ushio Electric Co., Ltd.) is used.
302 / 1MN: 302 / 5XX-DX01, using a mounted lamp UVL-30000M2-N1), 1 J / c
Irradiation with active energy rays of m ² was performed to cure. Liquid crystal is injected from the opening, and the opening is sealed with a sealing material (Loctite 350, UV-curable modified acrylate, manufactured by Nippon Loctite) to prevent air from entering, and sealed with the sealant of the present invention. The obtained liquid crystal panel was obtained. The sealant of the present invention is sufficiently cured under the above conditions, and is 1.5 kg / cm.
Even if the ^second pressure without the two glass plates is shifted,
The spacing was maintained at 7 μm.

[0074]

The composition for a sealing resin of the present invention is sufficiently cured by a small amount of active energy ray irradiation or by heating at a low temperature for a short time. The present invention is extremely useful in the field of electronics because resin sealing of a semiconductor chip having high reliability and excellent mass productivity, underfill for flip chip mounting, and sealing of a liquid crystal panel can be performed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01L 23/31 F-term (Reference) 4H017 AA04 AA31 AB07 AC08 4J005 AA07 AA11 BA00 BB01 BB02 4M109 AA01 BA04 CA05 EA03 EB02 EB04 EB07 EB08 EB09 EB12 EB18 EB19 EC20

Claims (16)

[Claims] 1. A composition for a sealing resin comprising a compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule. 2. The composition for a sealing resin according to claim 1, wherein the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule is an alicyclic alkane. object. 3. The compound according to claim 2, wherein the compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule includes a compound represented by the general formula (1). A composition for a sealing resin. Embedded image Wherein R is a hydrogen atom or a methyl group, and m is 0 to 2
N is 2 when m is 0, and 1 otherwise.) 4. A compound (a) having at least one oxetanyl group and at least one epoxy group in the same molecule, 7,8-epoxy-2-oxa-5-methyl-spiro [3.5] nonane and The composition for a sealing resin according to claim 3, further comprising 6,7-epoxy-2-oxa-spiro [3.5] nonane. 5. The composition for a sealing resin according to claim 1, further comprising a compound (b) that initiates cationic polymerization by irradiation with active energy rays and / or heating. 6. The compound according to claim 5, wherein the compound (b) that initiates cationic polymerization by irradiation with active energy rays and / or heating is at least one selected from a sulfonium salt, an iodonium salt and a diazonium salt. A composition for a sealing resin. 7. A compound (c) having at least one epoxy group and not having an oxetanyl group.
The composition for a sealing resin according to any one of the above. 8. A compound (d) having at least one oxetanyl group and not having an epoxy group.
The composition for a sealing resin according to any one of the above. 9. The composition for a sealing resin according to claim 1, further comprising a compound (e) having a radically polymerizable unsaturated group. 10. The composition for a sealing resin according to claim 1, further comprising a photoradical polymerization initiator (f). 11. The composition for a sealing resin according to claim 1, which is a composition for a semiconductor sealing resin. 12. The sealing resin composition according to claim 1, which is a liquid crystal panel sealing resin composition. 13. A cured product obtained by curing the composition for a sealing resin according to any one of claims 1 to 12. 14. The method for producing a cured product according to claim 13, wherein the composition for a sealing resin is cured by irradiation with active energy rays and / or heating. 15. The method for producing a cured product according to claim 14, wherein the active energy rays are ultraviolet rays. An apparatus sealed with a cured product of the composition for a sealing resin according to any one of claims 11 to 13.