WO1998031765A1

WO1998031765A1 - Adhesive composition and applications thereof

Info

Publication number: WO1998031765A1
Application number: PCT/JP1998/000136
Authority: WO
Inventors: Kazuhiko Ishii; Kiyohisa Tokuda; Kenji Yoshida; Minoru Yokoshima
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 1997-01-20
Filing date: 1998-01-16
Publication date: 1998-07-23

Abstract

An actinic radiation-curable adhesive composition suitable for bonding between opaque substrates in optical disks (particularly DVD and MO), IC cards and the like and applications thereof, that is, bonded articles, bonding methods, and a process for preparing optical disks; more specifically, an adhesive composition comprising a cationically photopolymerizable compound (A) having a low curing rate, a cationic photopolymerizable compound (B) having a high curing rate, and a cationic photopolymerization initiator (C); a bonding method characterized by coating the surface of at least one of two substrates with the above adhesive composition, irradiating the coated surface with an actinic radiation so that the content of the residual epoxy groups on the coated surface amounts to generally 50 to 95 %, and then bringing the coated surfaces into intimate contact with each other; and a process for preparing optical disks.

Description

Description Adhesive composition and its application Technical field ''

The present invention relates to an energy ray-curable adhesive composition suitable for bonding opaque substrates such as optical disks (particularly DVD, MO) and IC cards, and applications thereof, namely, an adhesive, a bonding method, and a bonding method. The present invention relates to a method for manufacturing an optical disk. Background art

Conventionally, as a method of bonding opaque substrates, a bonding method using heat has been adopted. Many of the bonding methods using heat use epoxy, melamine, urethane and acrylic resins and a thermosetting agent, and hot melt resins and the like are also known.

However, the bonding method using heat has a problem that the base material is warped or deformed by heat. In addition, hot-melt resins have poor thermal stability and poor weather resistance, making it difficult to use them in high-temperature environments.

The above-mentioned conventional bonding method by heat causes warpage and deformation of the base material, which causes a problem in productivity, and a solution to the problem is desired. Furthermore, in the bonding in the optical disc field where higher recording density is required, it is necessary to use a protective film or adhesive with more excellent characteristics for the adhesiveness, the warpage of the disc, and the protection and deformation of the recording layer. The problem remains. Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, even an opaque substrate can be cured at room temperature, and has adhesiveness, warpage of a disk, anti-corrosion and deformation resistance of a recording film, and resistance to deformation. The present invention has succeeded in providing an adhesive composition, an optical disk, and a method for producing the same, which are excellent in impact properties and the like. That is, the present invention relates to the inventions described in the following items 1 to 18. 1, energy beam polymerizable compound (A) with slow curing speed, energy beam with fast curing speed An adhesive composition comprising a polymerizable compound (B) and an energy ray polymerization initiator (C).

2. The energy beam polymerizable compound (A) with a slow curing rate is a glycidyl compound, the energy beam polymerizable compound (B) with a fast curing rate is an alicyclic ether compound, and an energy linear polymerization initiator (C 3. The adhesive composition according to the above item 1, wherein is an optical thione polymerization initiator.

3. The adhesive composition according to the above item 1 or 2, further comprising a polyol compound (D) having at least two hydroxyl groups in a molecule.

4. The adhesive composition according to the above item 3, wherein the polyol compound (D) having at least two hydroxyl groups in the molecule is a polyol having no acidic group.

5. The adhesive composition according to the above item 4, wherein the polyol having no acidic group is a polyester polyol or a polyprolactone polyol.

6. The adhesive composition according to the above items 3 to 5, wherein the molecular weight of the polyol is from 200 to 1,000.

7. The above items 1 to 4 wherein the content of the energy ray polymerization initiator (C) is 0.01 to 4 parts by weight based on the total amount (100 parts by weight) of the components (A) to (C). Item 7. The adhesive composition according to Item 6.

8. The above item 1 wherein the content of the energy ray polymerization initiator (C) is from 0.05 to 0.6 parts by weight based on the total amount of the components (A) to (C) (100 parts by weight). 7. The adhesive composition according to claim 6, wherein

9. The adhesive composition according to the above item 7 or 8, further comprising a filler (E).

10. Energy beam polymerizable compound (A) with slow curing speed, energy beam polymerizable compound (B) with fast curing speed, energy beam polymerization initiator (C), compound with at least two hydroxyl groups in the molecule (D ) And a filler (E), and the content of the component (A) is 5 to 50 parts by weight, and the total amount of the components (A), (B) and (D) is 100 parts by weight. The content is 5 to 90 parts by weight, the content of the component (D) is 5 to 50 parts by weight,

An adhesive composition characterized in that the content of the component (C) is 0.01 to 4 parts by weight and the content of the component (E) is 1 to 60 parts by weight. 1. Glycidyl compound, epoxidized alicyclic hydrocarbon, photoinitiated thione polymerization initiator (C), compound (D) having at least two hydroxyl groups in molecule, and filler (E), containing glycidyl The glycidyl compound content is 10 to 30 parts by weight, based on the total amount of the compound, the alicyclic hydrocarbon epoxidized product and the (D) component, 100 parts by weight, and the alicyclic hydrocarbon epoxidized product. Is 30 to 80 parts by weight, the content of the component (D) is 10 to 40 parts by weight, and the content of the component (C ′) is 0.05 to 0.5 part by weight. The adhesive composition according to claim 1, wherein the content of the component (E) is 1 to 60 parts by weight.

12. An adhesive having a cured product layer of the adhesive composition according to any one of the above items 1 to 6 and 8 to 11.

13. The adhesive according to the above item 12, wherein the adhesive is an optical disk.

14. The adhesive according to the above item 13, wherein the optical disk is MO or DVD.

15. The adhesive according to the above item 12, wherein the adhesive is an IC card.

16.After applying the adhesive composition according to the above paragraphs 1 to 6 or 8 to 11 on each or one of the two base materials, apply energy rays A bonding method characterized by irradiating the surfaces with each other, and then bringing the applied surfaces into close contact with each other or the surface of the other substrate not coated with the adhesive composition.

17, after applying the adhesive composition according to any one of the above-mentioned paragraphs 1 to 6, and 8 to 11 on each or one of the two substrates, the adhesive on the application surface The composition is irradiated with energy rays so that the residual ratio of epoxy groups in the composition is 50 to 95%, and then the coated surfaces or the coated surface and the adhesive composition are not coated. A bonding method characterized in that the surface of one of the base materials is brought into close contact.

18. Above paragraphs 1 to 6 and 8 to 11 above the recording layer of the optical disk substrate or, if there is a protective layer on the recording layer, on the protective layer. After applying the adhesive composition described above, the applied surfaces were irradiated with energy rays so that the residual ratio of epoxy groups in the applied adhesive composition was 50 to 95%, and then the applied surfaces were bonded to each other. A method of manufacturing an optical disc, which is characterized in that it is brought into close contact. BEST MODE FOR CARRYING OUT THE INVENTION

The adhesive composition of the present invention contains an energy ray polymerizable compound (A) having a slow curing rate, an energy ray polymerizable compound (B) having a fast curing rate, and an energy ray polymerization initiator (C). Examples of the energy rays include light, ultraviolet rays, X-rays and electron beams, and ultraviolet rays are preferred.

Considering the work efficiency and the like, the criteria for “high curing speed” and “low curing speed” of preferable energy ray polymerizable compounds are as follows.

For example, a compound with a maximum heat generation time (elapsed time from the start of heat generation to the peak) in an optical DSC of an ordinary energy ray polymerizable compound within 0.5 minutes belongs to a “fast” one, and a material with a time longer than 0.5 minutes It belongs to the "slow" one. Even if it is slow, the maximum heat generation time is preferably within 10 minutes, more preferably within about 5 minutes.

The measurement of the light DSC in the present invention is usually performed using the following apparatus and sample.

Equipment used: 910 Differential Scanning Calorimeter (Du Pont Instruments) Cell used: Part 9000786, 901 (TA Instruments)

UV irradiation: 3 mW / cm ²

Sample:: A composition obtained by adding 1 part by weight of a photopolymerization initiator to 100 parts by weight of an energy beam polymerizable compound.

Sample usage: approx. 3 to 4 mg

Energy radiation polymerization initiator used: UVI—6990 · (See note * 1 in Table 2 below)

Even if the maximum exothermic time is 0.5 minutes or more in the above measurement method, a compound is also preferable in which the maximum exothermic time in optical DSC is within 0.5 minutes when other energy ray-polymerizable compounds are added and used together. Fast ”belongs to the compound. Such compounds include, for example, compounds having an oxetane ring.

It should be noted that the above-mentioned division of the maximum heat generation time is a guide, and there may be some fluctuation as long as the object of the present invention is achieved.

Usually, "slow" includes, for example, glycidyl compounds, and "fast" Examples thereof include, but are not limited to, epoxidized alicyclic hydrocarbons.

A typical example of the energy ray polymerizable compound (A) having a low curing rate used in the present invention is a glycidyl compound. The glycidyl compound can be used without any particular limitation as long as it has a glycidyl group. Usually, a compound having a molecular weight of 75 or more, preferably 85 or more is used. Although there is no particular upper limit for the molecular weight, it is usually at most 100,000, preferably at most 5,000, more preferably at most 3,000. More specifically, for example, glycidyl ester compounds such as glycidyl ester of linoleic acid dimer and glycidyl ether compounds can be mentioned, and glycidyl ether compounds are preferable. These glycidyl compounds can be used alone or in combination of two or more.

Examples of the glycidyl ether compound include an aromatic glycidyl ether compound and an aliphatic glycidyl ether compound. Examples of the aromatic glycidyl ether compounds include 1,2-epoxy-12-butyl-3-phenoxypropane, 1,2-epoxy-13-methyl-13-phenoxypropane, and 1,3-bis (2,3-epoxypropoxy) benzene, 1,2-epoxy-13-phenoxypropane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolak epoxy resin, cresol · Novolak type epoxy resin. Examples of the aliphatic glycidyl ether compound include butylglycidyl ether, 1-aryloxy-1,2,3-epoxypropane, 1,4-butanedioldiglycidyl ether, triglycidyl ether of glycerol, and propylene glycol. Glycidyl ether, trimethylolpropane triglycidyl ether and the like.

Representative examples of the “energy beam polymerizable compound (B) having a high curing rate” used in the present invention include, for example, alicyclic ether compounds. The alicyclic ether compound is a cyclic ether compound excluding the glycidyl compound, and examples thereof include an epoxide of an alicyclic hydrocarbon and a compound having an oxetane ring. Examples of the epoxidized alicyclic hydrocarbon include a cycloaliphatic compound having an epoxy group (hereinafter, referred to as an alicyclic epoxy compound). Examples of the alicyclic epoxy compound include, for example, an alicyclic epoxy compound having, on a 4- to 7-membered cyclic aliphatic group, an epoxy group sharing one side with these rings, and having a molecular weight of 52 or more, Preferably, it is 100 or more. Although there is no particular upper limit for the molecular weight, it is usually 500 or less. The alicyclic epoxy compound preferably has 1 to 3 and more preferably 1 to 2 cycloaliphatic groups and epoxy groups, respectively, and preferably has 1 to 3 cycloaliphatic groups having an epoxy group. It has three, more preferably one or two. In the case of a compound having a plurality of cycloaliphatic groups having an epoxy group, the cycloaliphatic group may be directly bonded without using a crosslinking group, or may be bonded via a crosslinking group. The cross-linking group may be a branched or unbranched hydrocarbon chain having about 1 to 10 carbon atoms, which may contain a hetero atom (other than a nitrogen atom) other than carbon, such as oxygen or sulfur. Hetero atoms (excluding nitrogen atoms) such as oxygen and sulfur other than carbon can be exemplified. Specific compounds include, for example, compounds having one cycloaliphatic group having an epoxy group, compounds having no substituent on the ring other than the epoxy group, limonenedioxide, and 4-vinylcyclohexene monoamine. Compounds having an aliphatic hydrocarbon group having about 1 to 10 carbon atoms in addition to an epoxy group on an aliphatic ring such as an oxide. Compounds having a plurality of cycloaliphatic groups having an epoxy group include, for example, (3,4-epoxycyclohexyl) methyl-1,4-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclo). Xyl) adipate, bis- (2,3-epoxycyclopentyl) ether, (2,3-epoxy-6-methylcyclohexylmethyl) adipate, dicyclohexyl pendoxygenide and the like.

Examples of alicyclic ether compounds having an oxetane ring include 3-methyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxenylmethoxy) methyl] benzene and the like. Is raised.

Further, the above-mentioned polymer having an alicyclic ether group in a side chain is also included in the alicyclic ether compound in the present invention. As a polymer having such an alicyclic ether group in the side chain Examples thereof include homopolymers of 4-vinylcyclohexene monooxide and copolymers of 4-vinylcyclohexene monooxide with other monomers having an unsaturated double bond. .

One or more of these alicyclic ether compounds (B) may be used in combination.

Next, Table 1 shows a part of the measurement results of the optical D S C of representatives of the above compounds. Sample No. Energy ray polymerizable compound Maximum heat generation time

1. Diglycidyl ether of bisphenol A 0.8 min

2. Diglycidyl ether of hydrogenated bisphenol A 1.2 minutes

3. (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate 0.2 min

4. Bis- (3,4-epoxycyclohexyl) adipate 0.3 min

5. 1,4-bis [(3-ethyl-1-3-oxenylylmethoxy) methyl] benzene

(a) No other energy beam polymerizable compound used 3.0 min or more

(b) Use of other energy ray polymerizable compound 0.3 min

note)

Equipment used: 910 Differential Scanning Calorimeter (Du Pont Instruments) Cell used: Part 9000786, 901 (TA Instruments) '

UV irradiation: 3 mW / cm ²

Sample:

No. 1 to 5 (a): A composition obtained by adding 1 part by weight of a photopolymerization initiator to 100 parts by weight of an energy beam polymerizable compound

No. 5 (b): Composition obtained by adding 1 part by weight of a photopolymerization initiator to 5 parts by weight of another energy ray-polymerizable compound and 95 parts by weight of an energy ray-polymerizable compound

Sample usage: about 3-4mg Energy ray polymerization initiator used: UVI-6990 (See note * 1 in Table 2 below)

Other energy beam polymerizable compounds used: bis- (3,4-epoxycyclohexyl) adipate As the energy beam polymerization initiator (C), for example, a photo-induced thione polymerization initiator can be mentioned. Specific examples of the photodynamic thione polymerization initiator include, for example, 4,4'-bis [diphenylsulfonio] phenylsulfide-bis-hexafluoroantimonate and 4,4'-bis [diphenylsulfonate E) Phenylsulfide D-bis-hexafluorophosphate, 4,4-bis [di (?-Hydroxyethoxy) phenylsulfonio] phenylsulfido-bis-hexafluoroantimonate, 4,4'-bis

[Di (?-Hydroxyethoxy) phenylsulfonio] phenylsulfidobis-hexafluorophosphate, triphenylsulfoniumhexafluoroantimonate, 2,4-getyl-17- [di (p —Fluorophenyl) sulfonio] thioxanthonehexafluoroantimonate, 2-isopropyl-17- [di (p-fluorophenyl) sulfonyl] thioxanthonehexafluorophosphate, 1 —cloth 14-4 Propoxy-17- [diphenylsulfonio] thioxanthone hexafluoroantimonate. The photoinitiated thione polymerization initiator is usually used after being dissolved in lactone or propiocarbonate. The components (A) to (C) constituting the composition suitable for the adhesive of the present invention are usually used in an amount of 10 to 95% by weight of the total of the three components. Preferably 1

0 to 85% by weight, the content of the component (C) is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, still more preferably 0.05 to 1% by weight, Particularly preferably

0.05 to 0.6% by weight, with the balance being component (B), with a preferred content of 4.

It is at least 99% by weight, more preferably at least 14.99% by weight, even more preferably at least 34.9% by weight, and the upper limit is preferably at most 89.99% by weight, more preferably at most 8%.

9. 95% by weight or less, more preferably 84.9% by weight or less.

Considering the corrosiveness to metal, it is preferable that the content of the component (C) is small. The adhesive composition of the present invention may further contain a compound (D) having at least two hydroxyl groups in a molecule, a filler (E), and / or a lactone compound (F). Compounds having at least two hydroxyl groups in the molecule (D) ゃ The lactone compound (F) is mainly used to adjust the curing speed and to increase the flexibility and adhesion of the film. Considering the storage stability over time (pot life), a compound (D) having at least two hydroxyl groups in the molecule is preferable. The filler (E) is mainly used for imparting or improving the thixotropic property.

As the compound (D) having at least two hydroxyl groups in the molecule, a compound having no acidic group other than a phenolic hydroxyl group is preferable. For example, a polyol compound having no functional group other than a hydroxyl group (D-1) ), A polyester polyol compound (D-2), a polyhydric prolactone polyol compound (D-3), a polyol compound having a phenolic hydroxyl group (D-4), and a polycarbonate polyol. By using a compound (D) having at least two hydroxyl groups in the molecule, the formation of a film on the surface of the coating film after irradiation with energy rays can be more strongly suppressed, and the adhesion of the surface is not hindered. It is possible to obtain an adhesive having a non-uniform bonding surface. Further, a higher impact resistance can be imparted to an adhesive using the adhesive of the present invention.

Examples of the polyol compound (D_l) having no functional group other than the alcoholic hydroxyl group include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,9-nonanediol, and neopentyl. Glycol, tricyclo mouth decane dimethylol, cyclohexane dimethyl alcohol, trimethylol propane, glycerin, hydrogenated polybutene polyol, hydrogenated dimer diol, and other aliphatic polyols, diethylene glycol, tripropylene glycol, polyethylene glycol, Polypropylene glycol, polytetramethylene glycol, trimethylolpropane polyethoxytriol, glycerin polypropoxytriol, bisphenol A polyethoxydiol, bisphenol F polyethoxy Diol, an ether bond, such as Jitorimechiro one trimethylolpropane having one or two or more (poly) E one Teruporio - can be exemplified Le. Examples of the polyester polyol compound (D-2) include the above-mentioned polyol compound (D-1) having no functional group other than the alcoholic hydroxyl group and a polybasic acid (for example, maleic acid, succinic acid, adipic acid) Terephthalic acid, isophthalic acid, hydrogenated dimer acid) or a reaction product thereof with an anhydride thereof.

Examples of the polyforce prolactone polyol compound (D-3) include a reaction product of the above-mentioned polyol compound (D-1) having no functional group other than the alcoholic hydroxyl group and ε-force prolactone, Alternatively, a reaction product of the polyol compound (D-1) having no functional group other than the alcoholic hydroxyl group, the polybasic acid or an anhydride thereof, and ε-force prolactone can be used.

Examples of the polyol compound having a phenolic hydroxyl group (D-4) include compounds having at least two hydroxyl groups in a molecule, such as bisphenol, phenol novolak, and cresol novolak.

Examples of the lactone compound (F) include £ -force prolactone, arptyrolactone, and (5-valerolactone). Preferred examples thereof include £ -force prolactone and arbutyrolactone. it can.

Among these components (D), more preferred compounds include compounds having 2 to 5, more preferably 2 to 3, hydroxyl groups. Considering the temporal stability (pot life) of the composition, for example, acidic compounds such as a polyol compound (D-1) having no functional group other than an alcoholic hydroxyl group and a polyfunctional prolactone polyol compound (D-3) can be used. Polyols having no group can be mentioned. Among the polyol compounds (D-1) having no functional group other than the alcoholic hydroxyl group, a polyether polyol having two or more ether bonds is preferable. In addition, among the polyprolactone polyol compounds (D-3), a reaction product of a polyol compound (D-1) having no functional group other than the alcoholic hydroxyl group and a protolactone is preferred. More preferred compounds include, for example, polytetramethylene glycol, polyprolactone diol, and polyprolactone triol.

In the present invention, a filler (充填) can be further contained as necessary. The filler (E) is mainly used for imparting or improving thixotropic properties. By using the filler (E), thixotropy is imparted or improved, and the suitability for screen printing of the adhesive composition of the present invention can be enhanced.

Examples of the filler (E) include silicon dioxide, titanium dioxide, alumina, barium sulfate, kaolin, talc, clay, calcium carbonate, bentonite, glass fiber, carbon fiber, mica, and organic filler (eg, resin beads). And the like, known and commonly used fillers.

In the adhesive composition of the present invention, the use ratio of the components (D), (E) and (F) is as follows: the total amount of the components (A) to (C), and the component (D) , Preferably 0 to 60 parts, more preferably 0 to 50 parts, the component (F) is 0 to 60 parts, more preferably 0 to 50 parts, and the component (E) is (A) to (D), ( F) The amount is preferably 0 to 60 parts, more preferably 0 to 40 parts, based on 100 parts of the total amount of the components.

When the component (D) is used in addition to the components (A) to (C), the amount of the component (A), (B) and (D) is 100 parts by weight, and (A) is Preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, component (B) is preferably 5 to 90 parts by weight, more preferably 30 to 80 parts by weight, component (D) is preferably 5 to 90 parts by weight. 50 parts by weight, more preferably 10 to 40 parts by weight, and the component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 1 part by weight, particularly preferably 0.05 to 0.5 parts by weight. ~ 0.5 parts by weight. Further, when the component (E) is used, the amount used is preferably 1 to 6.0 parts by weight, more preferably 5 to 100 parts by weight based on the total amount of the components (A), (B) and (D). It is up to 40 parts by weight.

The composition of the present invention may further contain, if necessary, a cationic polymerizable substance other than the components (I) and (II), a (meth) acrylate compound, an ultraviolet absorber, an antioxidant, a leveling agent, A foaming agent, a polymerization inhibitor and the like can be used in combination. Cationic polymerizable substances other than the components (I) and (II) include, for example, η-butylvinyl ether, cyclohexyl vinyl ether, butanediol divinyl ether, triethylene glycol divinyl ether, and cyclohexyl. Sandimethylol divinyl ether, trimethylolpropane tribi Examples of vinyl ether compounds such as polyesters and the like, and examples of (meth) acrylate compounds include (meth) acrylate oligomers such as epoxy (meth) acrylate and (meth) acrylate monomers. Can be

The adhesive composition of the present invention can be prepared by mixing the above-mentioned components (A) to (E) and other components in an arbitrary order, or by mixing all of them together as appropriate. The bonded body of the present invention is obtained by bonding two substrates through a cured product layer of the above adhesive composition. The thickness of the cured product layer is preferably, for example, about 5 to 100 μm. The substrate is not particularly limited, but from the viewpoint of fully utilizing the function of the above-mentioned adhesive composition, it is usually 28 2ηπ! A substrate that does not transmit energy rays at a wavelength of up to 380 nm is preferable. For example, an optical disc substrate in which a recording layer made of a metal film such as aluminum is provided on a polycarbonate substrate is exemplified. . The two substrates may be the same or different.

In order to bond the two substrates, for example, the following may be performed. That is, the adhesive composition described above is applied to one or both surfaces of two same or different base materials by spinning, screen printing, etc., to a thickness of 5 to 100 μm, It is preferably applied to a screen printing machine or the like so as to have a thickness of 5 to 50 m, more preferably 10 to 30 m, and the residual ratio of epoxy groups in the applied adhesive composition (infrared absorption spectrum) The ratio of the amount of epoxy groups after irradiation with energy such as ultraviolet rays to the initial amount of epoxy groups quantified by a vector analysis method or the like is expressed as a percentage). Irradiates energy rays such as ultraviolet rays in the range of 60 to 90% (adjusts the energy of the energy rays such as ultraviolet rays). When the residual ratio of the epoxy group is 95% or more, curing is not sufficiently performed, and when the residual ratio is 50% or less, adhesiveness is deteriorated. Next, the surfaces irradiated with energy rays such as ultraviolet rays on the two substrates or one coated surface and the uncoated surface of the other substrate are bonded together, for example, at room temperature (about 20 ° C) or heated ( It may be left for about 0.5 to 24 hours at about 20 to 50 ° C). Bonding is possible even if the standing time is 0.5 hours or less. The optical disk of the present invention is obtained by bonding a substrate for an optical disk to another substrate via a cured product layer of the adhesive composition. The thickness of the cured product layer is, for example, 5 to 100 m The degree is preferred. An optical disc substrate is, for example, a substrate made of polycarbonate and provided with a recording layer made of a metal sputter film or the like, and does not normally transmit energy rays at a wavelength of 280 nm to 380 nm. Things. Other substrates include, for example, optical disk substrates. Examples of the optical disk of the present invention include MO (magneto-optical disk) and DVD (digital versital or video disk). Of these, double-sided reading type M0 and DVD and single-sided double-layer reading type DVD need to adhere non-transparent substrates to each other, in that the performance of the adhesive composition of the present invention is fully utilized. preferable.

In order to manufacture the optical disk of the present invention, for example, the following may be performed. That is, a protective layer (usually obtained by curing an ultraviolet-curable resin composition) on the recording layer of an opaque optical disk having a recording layer made of a metal such as aluminum or the like, or on the recording layer. ), The adhesive composition (in this case, also referred to as the adhesive composition for optical discs) is applied to a thickness of 5 to 100 mm using a spin coater or a screen printing machine. The remaining epoxy group in the applied adhesive composition (the epoxy group after irradiation with ultraviolet rays relative to the initial amount of epoxy groups determined by infrared absorption spectrum analysis, etc.) Is usually 50 to 95%, preferably 60 to 90%, and is irradiated with energy rays such as ultraviolet rays. When the residual ratio of the epoxy group is 95% or more, curing is not sufficiently performed, and when the residual ratio is 50% or less, adhesiveness is deteriorated. Then, the coated surfaces are adhered to each other, for example, at a room temperature (about 20 ° C) or a heated state (about 20 to 50 ° C) for 0.5 to 24 hours. The composition is cured, and the optical disk of the present invention can be obtained. When the curing speed of the adhesive composition is high, bonding is possible even when the standing time is 0.5 hour or less.

In the IC card of the present invention, a starting coil manufactured from an opaque substrate and a copper wire or the like coated with an IC chip and / or a polymer such as polyimide is provided via a cured film layer of the adhesive composition of the present invention. Are bonded together. Opaque substrates include, for example, sheets of polyvinyl chloride, polyethylene terephthalate, and polycarbonate containing a white pigment. This IC force is bonded to the opaque substrate and IC chip in the same manner as above. Manufactured. An IC card in which an opaque substrate and an IC chip are bonded is called a contact IC card, and an IC card in which an opaque substrate is bonded to an IC chip and a launch coil is called a non-contact IC card. Example '

Hereinafter, the present invention will be described more specifically with reference to examples.

Examples 1 to 7

(1) Preparation of adhesive composition and preparation of test piece (optical disk)

According to the composition shown in Table 2, these components were uniformly mixed to prepare an adhesive composition of the present invention (in Table 2, numerical values are parts by weight). The prepared adhesive composition is applied to a recording layer of an optical disc substrate having an aluminum vapor-deposited film as a recording layer by a screen printing method so as to have a thickness of 20 μm, and ultraviolet rays are applied to the coated surface. Irradiation, residual ratio of epoxy groups in each composition (The ratio of the amount of epoxy groups after irradiation with ultraviolet rays to the initial amount of epoxy groups on the coated surface, determined by UV absorption spectroscopy, is expressed in%) UV rays were applied so as to be 80% (Examples 1 to 3) and 90% (Examples 4 to 7), then the coated surfaces were stuck together and left at about 25 ° C for 24 hours. Then, a test piece (optical disk) was obtained.

Table 2

Example

1 2 3 4 5 6 7

, ノ Ρ Ρ 7

Snoeno Nore V So Ri No Nore

Ether 70 70 70

1 丄个 pcs

EOCN- 104 S * 5 40 35 11

(B) Ingredient

Dos (^ 4

Hexyl) Adhesive 30 30 30 40 40 35 56

, Then P TT

UVI-6990 氺 1 1.0 2.0 0.5 0.5 0.5

1 ^ U

(D) Ingredient

J J Π 9 Π S R 丄 1fi u 丄 u

Polytetramethylene glycol

(Molecular weight 6 50) 24

IJ No Kake 73

Silicon dioxide (Average particle size 5 /) 8

(F) Ingredient

7 One-butyrolactone 30 20

£ Pro-Lactone 20

Other ingredients

Modaf mouth 31.0 1.0 1.0 1.0 1.0 1.0 1.0 Note * UV-6990: manufactured by Union Carbide Co., Ltd. 4'-Bis [diphenylsulfonio] phenylsulfurido bis-hexafluorophosphate, 50% propylene carbonate diluted. Therefore, the added amount of component (C) is half of the indicated amount.

* 2 PC I-062: Nippon Kayaku Co., Ltd., photo-induced thione polymerization initiator 2-isopropyl-7- [di (p-fluorophenyl) sulfonio] thioxanthone hexafluorophosphate

* 3 Modaf Kuchiichi: Monsanto Chemical Co., Ltd., leveling agent

* 4 Epikoto 1001: Bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.

* 5 EOCN-104S: N-Crazol 'novolak epoxy resin manufactured by Nippon Kayaku Co., Ltd.

* 6 PLAXEL 205: Polycaprolactonediol manufactured by Daicel Chemical Industries, Ltd.

(2) Evaluation method

Using this test piece, the curability and durability were evaluated by the following methods, and the peel value was evaluated by the following method using the test piece described in the section of the peel test below.

(a) Curability test: The test piece was adhered, the bonded substrate was peeled off, and the surface condition was observed.

夕 · · · · Evening is not allowed ■

△ · · · · A little tack is recognized

X · · · · not cured at all

(b) Peel test: A PC (polycarbonate) 100 mm film and a PC board were bonded in the same manner as in the example. Using this test piece, the film was peeled at a speed of 30 graduations using a 90-degree peel tester (Model NK-PT-DA) manufactured by Nissin Kagaku Co., Ltd., and the peel value (g / cm) was measured. did. (The larger the value, the better the adhesion.) (c) Durability test: The test piece was observed after standing at 100 ° C. and 85% RH for 100 hours.

O · · · 'No abnormalities such as pinholes and warpage

△ · · · 'Pinholes, warpage, etc. are slightly observed

X ■ ·. 'Pinholes, warpage, etc. are seen all over

(3) Evaluation results

Table 3 shows the evaluation results obtained above. Table 3

Example

1 2 3 4 5 6 7

Epoxy group residual ratio (%) 80% 80% 80% 90% 90% 90% 90%

Curability 〇〇〇〇〇〇〇

Peel value (gZ cm) 40 35 45 50 80 70 100

Durability 〇〇〇〇〇〇〇

As is evident from Table 3, the adhesives (for example, optical disks) using the adhesive composition and the bonding method (for example, optical disk manufacturing method) of the present invention are all excellent in adhesiveness and durability. -Examples 8, 9

According to the composition shown in Table 4, the adhesive composition of the present invention was prepared in the same manner as described above (in Table 4, the numerical values are parts by weight). The prepared adhesive composition is applied on a recording layer of an optical disc substrate having an aluminum vapor-deposited film as a recording layer to a thickness of 20 m by a screen printing method, and the applied surface is irradiated with ultraviolet rays. The residual ratio of epoxy groups in each composition (based on the amount of epoxy groups at the initial stage of the coated surface, as determined by UV absorption spectroscopy) UV light is applied so that the ratio of the epoxy groups after irradiation with UV light is 80%), and the coated surfaces are stuck together and left at about 25 ° C for 24 hours. Test pieces (optical discs) were obtained. Then, the bonded substrates were evaluated using a Dupont impact tester (JISK 5400 8.3.2, load = 500 g, drop height = 50 cm, shooting type = 0.5 inch), and the appearance was observed. did. As a result, no peeling or the like was observed at all in Example 8, indicating that it had high impact resistance. Although the product of Example 9 also showed relatively good impact resistance, in this test, some partial peeling was observed.

In addition, the obtained test pieces were all excellent in curability, difficulty in peeling (beer value (g / cm)), durability and the like. Table 4

Example

8 9

(A) Ingredient

EOCN- 104 S 15 15

(B) Ingredient

Bis (3,4_epoxycyclo

Hexyl) adipate 60 60

(C) Ingredient

UV 1-6990 * 1 0.5 0.5

(D) Ingredient

Polyforce prolactone triol 25

(UCC TON—030 1)

(E) ingredient

Silicon dioxide (average particle size 5) 10 10 As is clear from the above results, when the adhesive composition of the present invention using the component (D) is used, an adhesive having higher impact resistance can be obtained. Industrial applicability

The composition and the bonding method suitable for the adhesive of the present invention provide an adhesive having excellent curability, excellent adhesiveness and durability, and a higher impact resistance by using the component (D) or the component (F). It can be used for manufacturing excellent optical discs because it has characteristics such as the ability to be imparted. Since the formation of a film on the surface of the coating film after irradiation with energy rays can be suppressed more strongly, and the adhesiveness of the surface is not hindered, an adhesive having a non-uniform bonded surface can be obtained. Further, the adhesive of the present invention further imparts or improves thixotropy by using a filler (E), and can improve the screen printability of the adhesive composition of the present invention.

Claims

The scope of the claims

1. An adhesive composition comprising an energy ray polymerizable compound (A) having a slow curing rate, an energy ray polymerizable compound (B) having a fast curing rate, and an energy ray polymerization initiator (C).

2. The energy beam polymerizable compound (A) having a slow curing rate is a glycidyl compound, the energy beam polymerizable compound (B) having a fast curing rate is an alicyclic ether compound, and an energy linear polymerization initiator (C 2. The adhesive composition according to claim 1, wherein is a photoinitiated thione polymerization initiator.

3. The adhesive composition according to claim 1 or 2, further comprising a polyol compound (D) having at least two hydroxyl groups in a molecule.

4. The adhesive composition according to claim 3, wherein the polyol compound (D) having at least two hydroxyl groups in the molecule is a polyol having no acidic group.

5. The adhesive composition according to claim 4, wherein the polyol having no acidic group is a polyether polyol or a polycaprolactone polyol.

6. The adhesive composition according to claim 3, wherein the polyol has a molecular weight of 200 to 1,000.

7. Claim 1, wherein the content of the energy ray polymerization initiator (C) is 0.05 to 5 parts by weight based on the total amount of the components (A) to (C) (100 parts by weight). 7. The adhesive composition according to claim 6, wherein

8. If the content of the energy ray polymerization initiator (C) is the total amount of the components (A) to (C) (100 7. The adhesive composition according to claim 1, wherein the adhesive composition is contained in a ratio of 0.05 to 0.6 parts by weight with respect to (parts by weight).

9. The adhesive composition according to claim 7, further comprising a filler (E).

10. Energy linear polymerizable compound (A) with slow curing rate, energy beam polymerizable compound (B) with fast curing rate, energy ray polymerization initiator (C), Compound with at least two hydroxyl groups in the molecule (D ) And filler (E), and the content of component (A) is 5 to 50 parts by weight, and the total amount of component (A), (B) and (D) is 100 parts by weight. The content is 5 to 90 parts by weight, the content of the component (D) is 5 to 50 parts by weight,

An adhesive composition characterized in that the content of the component (C) is 0.01 to 4 parts by weight and the content of the component (E) is 1 to 60 parts by weight.

11. A glycidyl compound containing a glycidyl compound, an epoxidized alicyclic hydrocarbon, a light-powered thione polymerization initiator (C), a compound having at least two hydroxyl groups in a molecule (D), and a filler (E); The glycidyl compound content is 10 to 30 parts by weight and the alicyclic hydrocarbon epoxidation content is 30 parts by weight based on 100 parts by weight of the total amount of the epoxidized alicyclic hydrocarbon and the component (D). -80 parts by weight, the content of the component (D) is 10 to 40 parts by weight, the content of the component (C,;) is 0.05 to 0.5 part by weight, and the content of the component (E) is 1 to 60 parts by weight of an adhesive composition.

12. An adhesive having a cured product layer of the adhesive composition according to any one of claims 1 to 6, and 8 to 11.

13. The adhesive according to claim 12, wherein the adhesive is an optical disk.

14. The adhesive according to claim 13, wherein the optical disk is an MO or a DVD.

15. The adhesive according to claim 12, wherein the adhesive is an IC card.

16. After applying the adhesive composition according to claims 1 to 6 or 8 to 11 on each or one of the two substrates, The method of claim 1, further comprising irradiating the coated surfaces with each other, and then bringing the applied surfaces into close contact with each other or the surface of the other substrate not coated with the adhesive composition.

17, after applying the adhesive composition according to claims 1 to 6 or 8 to 11 on each or one of the two substrates, Irradiation is performed so that the residual ratio of epoxy groups in the adhesive composition becomes 50 to 95%, and then the applied surfaces are not applied to each other or between the applied surfaces and the adhesive composition. A bonding method characterized in that the surface of one of the base materials is brought into close contact.

18. Claims 1 to 6 and 8 to 1 above the recording layer of the optical disk substrate or, if there is a protective layer on the recording layer, on the protective layer. After applying the adhesive composition according to item 1, the applied surface is irradiated with energy rays so that the residual ratio of epoxy groups in the applied adhesive composition becomes 50 to 95%, A method for manufacturing an optical disk, characterized in that the coated surfaces are brought into close contact with each other.