JP2000343652A - Composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a composite strongly bonded to the surface of a silicone material and not generating falling-off or damage even during long-term use. SOLUTION: The surface of a silicone material is modified and subsequently coated with photo-setting α-cyanoacrylate and the coated silicone material is irradiated with light to obtain a composite wherein the silicone material and the α-cyanoacrylate resin layer are integrally bonded. Or, the surface of the silicone material is modified to be laminated to other material by using photo-sitting α-cyanoacrylate and the resulting laminate is irradiated with light to obtain a composite wherein the silicone material, the α-cyanoacrylate resin layer and other material are integrally bonded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite in which a silicone-based material such as silicone rubber or silicone resin and a curable resin are laminated, and more particularly, to a method for use in a switch of an electronic device such as a mobile phone. The present invention relates to a method for producing a composite in which a silicone rubber and a curable resin are integrally laminated.

[0002]

2. Description of the Related Art Conventionally, silicone-based materials such as silicone rubber and silicone resin have been widely used in industry because of their good weather resistance and durability. In particular, it is used in various products including electronic devices because it has a soft and flexible feeling of low contamination and a soft touch to the human body. On the other hand, this silicone-based material has a drawback that it is inferior in scratch resistance such as being easily scratched on the surface because it is flexible and elastic.
Therefore, for the purpose of improving this, a surface is coated with a curable resin material, or a hard plastic or the like is bonded with an adhesive. In addition, a silicone key switch material used particularly for a contact of an electronic device may require a soft touch and a reliable click feeling during operation in addition to the above-mentioned purpose. A curable resin layer was formed on the switch surface, and this was cured and bonded for use.

[0003] However, these silicone materials are generally difficult-to-adhere materials, and in particular, lack adhesion to different types of materials.
Adhesion with an adhesive is difficult, and peeling may occur for long-term use. In addition, the contact rubber used for the switch section of the electronic device is constantly applied with the impact of the pressing of the finger during use, so that the contact rubber is particularly likely to be peeled off, and a highly durable contact rubber cannot be obtained. Therefore,
Adhesion (adhesion) between this silicone material and other materials
Various improvements have been made to improve. For example, JP-A-5-325701, JP-A-6-5151,
JP-A-6-187871, JP-A-6-223671, JP-A-9-248881, JP-A-9-249759, and the like disclose a method of activating the surface of a silicone-based material by corona discharge or irradiation with short-wave ultraviolet light. Or, a method of applying a primer such as a silane coupling agent to modify the surface, a method using a visible light resin, and a method of combining and treating these, and the like, such as a method of combining a silicone material with another material. Methods for improving adhesion are disclosed.

[0004]

However, using any of the conventional methods, the adhesion between the silicone-based material and other materials is poor, and there has been a problem such as falling off or breakage due to long-term use. Therefore, an object of the present invention is particularly to produce a composite which adheres firmly to the surface of a silicone-based material and does not fall off or break even after long-term use.

[0005]

Therefore, in the present invention, the surface of a silicone material is modified, then a photocurable α-cyanoacrylate is applied, and then the silicone material is irradiated with light. The composite in which the α-cyanoacrylate resin layer is integrally adhered, the surface of the silicone material is modified, and then the photocurable α
-Solving the above-mentioned problems by a composite in which a silicone material, an α-cyanoacrylate resin layer, and other materials are integrally bonded by bonding other materials and the like using cyanoacrylate and performing light irradiation. did.

More specifically, the surface of the silicone-based material is activated by plasma discharge, short-wavelength ultraviolet irradiation, primer treatment, or a combination thereof, and then the photocurable α-cyano is applied. By applying an acrylate resin and irradiating light, a composite in which a silicone material and an α-cyanoacrylate resin layer are integrally bonded is obtained. If this method is used, for example, when another material is bonded to the silicone material, it is not necessary to use another adhesive to fix the position to prevent the displacement until the required actual bonding.

As the silicone-based material usable in the present invention, conventionally known materials can be used, and more specifically, a silicone rubber molded product molded by injection molding, compression molding, extrusion molding, or the like, or applied to a substrate or the like. And the like.

The photocurable α-cyanoacrylate adhesive composition used in the present invention is represented by the general formula (2): H ₂ C = C (CN) -COOR
(2) (In the formula, R is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. The carbon number of the ester residue is not particularly limited, but is usually Those having 1 to 8 carbon atoms may be used, and ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups may also be used.) To the composition,
-Generally obtained by adding a catalyst capable of polymerizing and curing the cyanoacrylate monomer.
For example, examples of the α-cyanoacrylate-based adhesive composition provided with photocurability of the present invention include the following 1) to
Examples such as 4) are given.

1) (A) α-cyanoacrylate (B) A transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electron-based ligand, α-cyanoacrylate containing (A) and (B) A cyanoacrylate adhesive composition. 2) (A) α-cyanoacrylate (B) Transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electron-based ligand (C) The above (A) to (C) of the cleavage type photoinitiator An α-cyanoacrylate adhesive composition containing: 3) (A) α-cyanoacrylate (B) An α-cyanoacrylate adhesive composition containing the above (A) and (B) of a platinum (II) acetylacetonate complex. 4) (A) α-cyanoacrylate adhesive composition (B) An α-cyanoacrylate-based adhesive composition containing the above-mentioned (A) and (B) of a specific metal complex salt that releases a nucleophile upon irradiation with light.

Next, the α-cyanoacrylate adhesive composition having photocurability used in the present invention,
-The cyanoacrylate monomer will be described in detail. The α-cyanoacrylate monomer is a monomer represented by the following general formula (2), wherein H ₂ C = C
(CN) -COOR (2) (wherein, R is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. Although the number is not particularly limited, those having 1 to 8 carbon atoms are usually used, and ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used.) As methyl α
Alkyl and cycloalkyl α-cyanoacrylates such as cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, cyclohexyl α-cyanoacrylate, allyl α-cyanoacrylate, methallyl α-cyanoacrylate, Alkenyl and cycloalkenyl α-cyanoacrylates such as cyclohexenyl α-cyanoacrylate, alkynyl α-cyanoacrylates such as propargyl α-cyanoacrylate, phenyl α-cyanoacrylate, aryl α-cyanoacrylate such as toluyl α-cyanoacrylate, hetero Atom-containing methoxyethyl α-cyanoacrylate, ethoxyethyl α-cyanoacrylate, furfuryl α-cyanoacrylate, silicon-containing Limethylsilylmethyl α-cyanoacrylate, trimethylsilylethyl α-
Examples include cyanoacrylate, trimethylsilylpropyl α-cyanoacrylate, and dimethylvinylsilylmethyl α-cyanoacrylate.

Next, as a catalyst for imparting photocurability to the above-mentioned α-cyanoacrylate monomer, for example, the following (a) transition of Group VIII of the periodic table containing an aromatic electron-based ligand: A mixed catalyst of a metal metallocene compound, (b) a transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electron ligand and a cleavage type photoinitiator, and (c) platinum (II) acetylacetate. Nart complex (d)
Specific metal complex salts that release a nucleophile upon irradiation with light are exemplified.

The above-mentioned (a) a transition metal group metallocene compound belonging to Group VIII of the periodic table containing an aromatic electron-based ligand is a compound represented by the following general formula (3).

[0013]

Embedded image

(Wherein M represents a transition metal of Group VIII of the periodic table. R represents a halogen atom or a carbon atom having 1 to 2 carbon atoms.
0 represents a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group or a phosphorus-containing group. Each R may be the same or different, and R may be crosslinked. A represents an integer of 0 to 5. Each [Ra-Cp] group (Cp represents η-cyclopentadienyl) may be the same or different. )

The aromatic electron ligand of the metallocene group VIII transition metal compound of the periodic table is not particularly limited, but preferably includes π-arene, indenyl and η-cyclopentadienyl. However, η-cyclopentadienyl is more preferably used. Further, as a substituent bonded to each ligand, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. Groups or phosphorus-containing groups. Each substituent may be the same or different, and the substituents may be cross-linked.

The periodic table containing an aromatic electron ligand
As the transition metal of the Group VIII transition metal metallocene compound,
Iron, osmium, ruthenium, cobalt or nickel are particularly preferred. Specific examples of the transition metal group VIII transition metal metallocene compound containing an aromatic electron ligand used in the present invention include the following compounds,
One of these may be used alone, or a mixture of several types may be used. As specific compounds, substances described in JP-A-10-88070 can be used.

Next, in the mixed catalyst (b) of the transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electron ligand used in the present invention and a cleavage type photoinitiator,
The transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electron-based ligand is the same as that described in detail in (a) above, and the cleavage type photoinitiator is described below. The photoinitiators of (1) to (3) shown are mentioned, and these can be used alone or in combination of several kinds. (1) As acetophenone-based photoinitiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2
-Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4
-(Methylthio) phenyl) -2-morpholinopropane-1 (2) benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl methyl ketal as a benzoin-based photoinitiator (3) Other light As an initiator, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,2 ′
-Azobis (2-methylbutyronitrile)
Platinum (II) acetylacetonate complex for imparting photocurability to a cyanoacrylate adhesive composition is defined as P
t (acac) ₂ . The specific metal complex salt that releases a nucleophile by light irradiation for imparting photocurability to the α-cyanoacrylate-based adhesive composition is trans- [Cr (NH ₂ ) ₂ (NCS) ₄ ].
^{_{- trans- [Cr (en) 2}} (NCS) 2] + trans- [Co (en) 2 Cl 2] + trans- [Cr (cyclam) Cl 2] + trans- [Cr (cyclam) (NCS) 2]
_{^{+ Trans- [Co (cyclam) Cl}} 2] + , and the like. Where en is ethylenediamine, c
yclam represents 1,4,8,11-tetraazacyclotetradecane.

The mixing ratio of the α-cyanoacrylate monomer of the photocurable α-cyanoacrylate adhesive composition used in the present invention to the above-mentioned catalyst is sufficient for photopolymerizing the α-cyanoacrylate monomer. The amount is not particularly limited as long as it is added.
When a transition metal metallocene compound of Group VIII of the periodic table containing an aromatic electron ligand of
It is suitable to add 0000 ppm, preferably 30 to 50,000 ppm. The amount of the cleavage photoinitiator (b) depends on the type and amount of the metallocene compound, but is generally 100 to 20,000 ppm, preferably 300 to 20,000 ppm, based on the α-cyanoacrylate monomer.
Used in the 15000 ppm range.

The photocurable α-cyanoacrylate-based adhesive composition used in the present invention may further contain a radical polymerizable compound such as an acrylate ester. Add specific additives such as anionic polymerization inhibitors, radical polymerization inhibitors, thickeners, curing accelerators, plasticizers, tougheners, fragrances, dyes, pigments, fillers, etc. and heat stabilizers as necessary. Can also.

An anionic polymerization inhibitor is added to increase the stability of the composition during storage. Examples of known inhibitors include sulfur dioxide, sulfur trioxide, nitric oxide, hydrogen fluoride and p-toluenesulfonic acid, and the like.
Generally 0.1 to 1000 for cyanoacrylate
It is added in the range of 0 ppm. Examples of the radical polymerization inhibitor include quinone, hydroquinone, t-butylcatechol, p-methoxyl-phenol, and the like.
It is added in the range of 10,000 ppm. In addition, thickeners are added to increase the viscosity of the composition. Examples of the thickener include poly (methyl) methacrylate, methacrylate type copolymer, acrylic rubber, cellulose derivative, polyvinyl acetate, and poly (α-cyanoacrylate). Many other conventional polymer additives are also added for toughness.
Examples include acrylic elastomers, acrylonitrile copolymer elastomers, fluoroelastomers, and fine silica fillers. These substances are
Also functions as a thickener.

Examples of the method for modifying the surface of a silicone material by irradiation with energy rays used in the present invention include, for example, JP-A-5-325701, JP-A-6-5151, and
Modification methods such as corona discharge and irradiation with short-wavelength ultraviolet light, which are disclosed in Japanese Patent Nos. 187871 and 6-223671, can be cited.

The present invention further proposes a method for modifying the surface of a silicone material by applying a primer. As the primer used here, conventionally known primers can be used, but the following compounds are preferably effective. As an example, the following general formula (1) R ₁ -N (R ₂ ) -R ₃ -OH (1) (wherein, R ₁ and R _{2 each} have 1 to 1 carbon atoms) 3 wherein R ₃ represents an alkylene group having 1 to 12 carbon atoms). Specific examples of the primer include 2-dimethylaminoethanol, 4-dimethylamino-1-butanol, diethylaminobutanol, 3-dimethylamino-1-propanol, 4-diethylaminopropanol, dimethylaminopentanol, diethylaminopentanol, -Dimethylamino-1-hexanol, 6
-Dimethylamino-1-hexanol, diethylaminohexanol, dimethylaminoheptanol, diethylaminoheptanol, 2- (2-diethylaminoethoxy) ethanol and the like.

As another primer that can be used in the present invention, a primer comprising a mixture of the following (a) and (b) can be used. (A) A compound selected from the group consisting of a benzene ring compound having an aldehyde group and a nitrogen or oxygen atom-containing heterocyclic compound having an aldehyde group. (B) Organic amine compounds These primers are compounds disclosed in JP-A-63-125585. Examples of the component (a) include benzaldehyde, dimethylaminobenzaldehyde, diethylaminobenzaldehyde, p-dimethylbenzaldehyde, aminobenzaldehyde, and terephthalate. Aldehyde, acetaldehyde aniline, propionaldehyde aniline, butyraldehyde aniline, pentyl aldehyde aniline, hexyl aldehyde aniline, pentaaldehyde aniline, 2-pyridinecarboxaldehyde, 2,6-pyridinecarboxaldehyde, pyrrole 2
-Carboxy sulfide, furfural and the like.

The component (b) is an organic amine compound having an OH group and an amino group in the molecule simultaneously,
Specific examples include dimethylaminopropanol, diethylaminopropanol, diethylaminopentanol, dimethylaminohexanol, 2-dimethylamino-2-methylpropanol, and the general formula R (NH ₂ )
₂ (where R is CnH ₂ n, n = 1 to 10), specifically, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, etc. In addition, diethylenetriamine, triethylenetetramine, N-methyldiethanolamine and the like are used.

These primer components may be used alone or as a mixture of two or more kinds. Generally, 0.1 part by weight or more, preferably 0.1 part by weight, per 100 parts by weight of a solvent such as acetone, dichloromethane, methanol and the like. -10 parts by weight are added and used.

It is also possible to use the above-described modification method by corona discharge or irradiation with short-wavelength ultraviolet rays together with the modification method by primer application.

[0027]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0028]

Examples 1 to 5 and Comparative Example 1 FIGS.
After applying a primer to the surface of the silicone sheet molded in a key switch shape as shown in FIG. 1 and evaporating the solvent, applying a photocurable α-cyanoacrylate, and then bonding a transparent polycarbonate keytop, Irradiation with light cured the α-cyanoacrylate. As Comparative Example 1, the same operation was performed without applying the primer.

The primer was prepared by adding 6-dimethylamino-1-hexanol (hereinafter referred to as DM) to 100 parts by weight of acetone.
AH) was added and adjusted in parts by weight shown in Table 1. As α-cyanoacrylate with photocurability,
Using TB1743 (main component: ethyl α-cyanoacrylate) manufactured by Three Bond Co., Ltd.
00 parts by weight of diacetylferrocene (hereinafter referred to as (AcC
_p) referred to as 2 Fe) was added 0.1 part by weight adjustment. The ultraviolet irradiation device used for photocuring was a 4 kW high-pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd.), and light irradiation was performed from a distance of 15 cm. The integrated light amount at the time of light irradiation was 1000 mJ / cm ² . Table 1 shows the results.

[0030]

[Table 1]

The adhesiveness of the cured product was evaluated by applying a force in the peeling direction to break the silicone material after photo-curing (material breakage). ◎ mark, applying a force in the peeling direction and not peeling easily (interfacial fracture). ) Is marked with ○, and the case where a force is applied in the peeling direction and the film is relatively easily peeled is marked with △. In addition, the case where almost no adhesion was made was represented as x. As apparent from Table 1, by applying the primer, the cured product strongly adhered to the silicone-based material.

[0032]

Examples 6 to 10 The same tests as in Examples 1 to 5 were performed as in Examples 6 to 10 except that the primer components were changed. As Comparative Example 2, a silane coupling agent (KBM manufactured by Shin-Etsu Chemical Co., Ltd.)
-403) was used. Each primer component is acetone 1
The compound shown in Table 2 was added in an amount of 1.0 part by weight with respect to 00 parts by weight, and adjusted. Table 2 shows the results. As is clear from Table 2, by applying the primer, the cured product was strongly adhered to the silicone material similarly to DMHA and could not be easily peeled off. However, when the silane coupling agent was used, it could be peeled off relatively easily.

[0033]

[Table 2]

[0034]

Examples 11 to 16 The same tests as in Examples 1 to 5 were performed as in Examples 11 to 16 except that the primer components were changed.
Primer is 100 parts by weight of acetone and component (a)
The components (b) were adjusted by adding the compounds shown in Table 2 in parts by weight. Table 3 shows the results. As apparent from Table 3, by applying the primer, the cured product adhered firmly to the silicone material and could not be easily peeled off.

[0035]

[Table 3]

[0036]

Examples 17 to 19 The same tests as in Examples 1 to 5 were performed as in Examples 17 to 19 except that the primer components were changed.
The primer was prepared by adding 1.0 part by weight of a compound shown in Table 4 to 100 parts by weight of acetone. Table 4 shows the results.
Shown in As apparent from Table 4, by applying the primer, the cured product adhered to the silicone material, but could be peeled off relatively easily.

[0037]

[Table 4]

[0038]

Examples 20 to 24 As Examples 20 to 24, the same tests as in Examples 1 to 5 were conducted by adjusting photo-curable α-cyanoacrylate as shown in Table 5. The primer was prepared by adding 1.0 part by weight of DMAH to 100 parts by weight of acetone. Table 5 shows the results. As is clear from Table 5, the cured product could not be easily removed from the silicone material.

[0039]

[Table 5]

[0040]

Examples 25 and 26 As Example 25, as shown in FIG. 2, a primer was applied to the surface of a silicone sheet, and after the solvent was volatilized, α-cyanoacrylate having photocurability was applied and cured by irradiating light. I let it. In Example 26, light irradiation was not performed. The primer was prepared by adding 1.0 part by weight of DMAH to 100 parts by weight of acetone. As α-cyanoacrylate with photocurability,
Using TB1743 (main component: ethyl α-cyanoacrylate) manufactured by Three Bond Co., Ltd.
0.005 parts by weight of ethyl ferrocene and 0.2 parts by weight of APO (acyl phosphine oxide) as a cleavage type photoinitiator were added to 00 parts by weight. The UV irradiation device used for photocuring was a 100 W high-pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd.), and light irradiation was performed from a distance of 10 cm.
The integrated light amount at the time of light irradiation was 100 mJ / cm ² . Table 6 shows the results. The evaluation method is in accordance with Examples 1 to 5.

As can be seen from Table 6, Examples 25 and 2
In both cases, the adhesion of the polycarbonate key top was good. However, after being stored in a dark place for 24 hours after bonding, the appearance was visually observed.
In No. 6, whitening occurred because the vapor of the α-cyanoacrylate monomer adhered to the periphery of the bonded portion. This is considered to be because the monomer of α-cyanoacrylate was not completely cured only by moisture in the air because no light irradiation was performed, and the uncured monomer evaporated and adhered to the surroundings.

[0042]

Examples 27 and 28 Using the compositions used in Examples 2 and 25, an adhesion test was performed according to each Example. However, irradiation was performed for 60 seconds from a distance of 5 cm using a 20 W black light fluorescent lamp (manufactured by Toshiba Lighting & Technology Corp.) instead of the ultraviolet irradiation device (high pressure mercury lamp). In addition to the adhesiveness, the appearance after storage in a dark place for 24 hours was visually observed as in Example 25. Table 6 shows the results. As can be seen from Table 6, there was no problem in the adhesiveness and the appearance after storage.

[0043]

[Table 6]

[0044]

According to the present invention, by modifying the surface of a silicone-based material, and then applying photocurable α-cyanoacrylate, and then irradiating with light, the two are firmly adhered to each other and extremely hardly peeled off. A composite can be manufactured.

In particular, the surface modification of the silicone-based material is performed by a primer R ₁ -N (R ₂ ) -R ₃ -OH represented by the following formula (1) (1) , R ₁ and R ₂ are an alkyl group having 1 to 3 carbon atoms, and R ₃ is an alkylene group having 1 to 12 carbon atoms) and a primer comprising the following two components: (a) a benzene ring having an aldehyde group Compounds and compounds selected from the group of nitrogen or oxygen atom containing heterocyclic compounds having an aldehyde group. (B) By using an organic amine compound, the adhesion to α-cyanoacrylate can be extremely increased.

Further, a lamp used for light irradiation for curing the photocurable α-cyanoacrylate is as follows:
Since inexpensive black light used in ordinary households can be as low as possible in illuminance, the light irradiation device itself used for photo-curing can be very inexpensive, and the cost merit is very large. The risk of exposure to water is also reduced.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a silicone key switch member.

FIG. 2 is a cross-sectional view of a silicone key switch member.

[Explanation of symbols] Silicone key switch Primer layer α-cyanoacrylate cured layer Polycarbonate key top

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 4/04 C09J 4/04 5/02 5/02 H01H 11/00 H01H 11/00 E // C08L 83 : 00 F-term (reference) 4F073 AA01 BA33 CA21 CA45 4F100 AH02A AH03A AH07A AH08B AK01C AK25B AK45 AK52A AN02 AT00C BA02 BA03 BA07 BA10A BA10C CC00A EH461 EH462 EJ082 EJ542 EJ651B38 J084J38J38J38 PC07 PC08 4J040 FA121 HD41 JB08 KA13 LA06 MA10 NA19 PA04 PA05 PA15 PA32 5G023 AA12 CA50

Claims (20)

[Claims] 1. A silicone-based material having a surface modified, α
-A composite composed of two or more cyanoacrylate-based resin layers. 2. A method for modifying the surface of a silicone-based material and then applying α-cyanoacrylate provided with photocurability,
The composite according to claim 1, wherein the silicone-based material and the α-cyanoacrylate resin layer are integrally bonded by performing light irradiation. 3. The irradiation light for curing the photocurable α-cyanoacrylate in the near-ultraviolet region.
The conjugate of claim 1. 4. The irradiated near-ultraviolet light is 1000 mJ / c.
4. The composite according to claim 3, wherein m is ² or less. 5. The composite according to claim 2, wherein the photocurable α-cyanoacrylate is an α-cyanoacrylate containing the following (A) and (B) as main components. (A) α-cyanoacrylate (B) Periodic Table VIII containing aromatic electron-based ligand
Group transition metal metallocene compounds 6. The composite according to claim 2, wherein the photocurable α-cyanoacrylate is an α-cyanoacrylate having the following (A) to (C) as main components. (A) α-cyanoacrylate (B) Periodic Table VIII containing aromatic electron-based ligand
Group transition metal metallocene compounds (C) Cleavable photoinitiators 7. The method according to claim 1, wherein the surface of the silicone material is modified by short-wavelength ultraviolet irradiation or corona discharge.
3. The composite according to any one of claims 1 to 2. 8. The composite according to claim 1, wherein the surface of the silicone material is modified by applying a primer. 9. The complex according to claim 8, wherein the primer mainly comprises a compound represented by the following formula (1). R ₁ -N (R ₂ ) -R ₃ -OH (1) (where R ₁ and R ₂ are an alkyl group having 1 to ₃ carbon atoms, and R ₃ is a 1 to 12 carbon atom. Represents an alkylene group) 10. The complex according to claim 8, wherein the primer comprises the following components (a) and (b) as main components. (A) A compound selected from the group consisting of a benzene ring compound having an aldehyde group and a nitrogen or oxygen atom-containing heterocyclic compound having an aldehyde group. (B) Organic amine compounds 11. A silicone material having a modified surface, α
-A composite comprising a cyanoacrylate-based resin layer and a three-layer structure or more of other materials. 12. The silicone-based material is modified by applying a photocurable α-cyanoacrylate to the surface of the silicone-based material, applying the cured product to another material, and then irradiating the material with light. -The cyanoacrylate resin layer and another material are integrally bonded.
The conjugate of claim 1. 13. The composite according to claim 12, wherein the irradiation light for curing the photocurable α-cyanoacrylate is in the near ultraviolet region. 14. Irradiation of near-ultraviolet light of 1000 mJ /
The composite according to claim 13, which has a size of not more than cm ² . 15. The composite according to claim 12, wherein the photocurable α-cyanoacrylate is an α-cyanoacrylate containing the following (A) and (B) as main components. (A) α-cyanoacrylate (B) Periodic Table VIII containing aromatic electron-based ligand
Group transition metal metallocene compounds 16. The composite according to claim 12, wherein the photocurable α-cyanoacrylate is an α-cyanoacrylate containing the following (A) to (C) as main components. (A) α-cyanoacrylate (B) Periodic Table VIII containing aromatic electron-based ligand
Group transition metal metallocene compounds (C) Cleavable photoinitiators 17. The composite according to claim 11, wherein the surface of the silicone material is modified by short-wavelength ultraviolet irradiation or corona discharge. 18. The composite according to claim 11, wherein the surface of the silicone material is modified by applying a primer. 19. The complex according to claim 18, wherein the primer mainly comprises a compound represented by the following formula (1). R ₁ -N (R ₂ ) -R ₃ -OH (1) (where R ₁ and R ₂ are an alkyl group having 1 to ₃ carbon atoms, and R ₃ is a 1 to 12 carbon atom. Represents an alkylene group) 20. The primer according to claim 18, wherein the primer comprises the following components (a) and (b) as main components.
The conjugate of claim 1. (A) A compound selected from the group consisting of a benzene ring compound having an aldehyde group and a nitrogen or oxygen atom-containing heterocyclic compound having an aldehyde group. (B) Organic amine compounds