JP2005281535A - Adhesive composition for optical device and optical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for an optical device, having an excellent heat resistance and durability even in the case of bonding members having different linear expansion coefficients. <P>SOLUTION: This adhesive composition for the optical device contains (A) a polymer of which main chain contains an acrylic acid alkyl ester monomer unit and/or a methacrylic acid alkyl ester monomer unit and at least one hydrolyzable silicon-containing group in one molecule and (B) a silane-coupling agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive composition for optical devices and an optical device. Specifically, it is suitable for manufacturing displays such as CRT, plasma display panel (PDP) and projection television (PTV), scanners, laser beam printers, digital copiers and other office automation equipment, condensing panels and solar cell modules. The present invention relates to an optical device adhesive composition for use in an optical device and an optical device bonded using the optical device adhesive composition.

  Conventionally, hot-melt adhesives such as EVA (ethylene-vinyl acetate copolymer), pressure-sensitive adhesives, pressure-sensitive adhesive tapes, and the like are often used for bonding members such as glass and resin. However, hot melt adhesives cannot be used for bonding heat-sensitive plastics or the like because the adhesive must be melted at the time of bonding. Moreover, since an adhesive and an adhesive tape have a problem in heat resistance and durability, they cannot be used in fields where these performances are required.

On the other hand, the photocurable adhesive composition is a one-component solventless adhesive that is cured by light, and can be cured at room temperature, so that it can be adhered to heat-sensitive plastics and the like.
However, the conventional photo-curable adhesive composition has good heat resistance and durability in bonding members having the same linear expansion coefficient, such as glasses or resins such as acrylic resins, but the glass and the resin Adhesion of members having different linear expansion coefficients such as adhesion and adhesion between metal and resin has problems of heat resistance and durability.

  In contrast, Patent Document 1 discloses urethane (meth) acrylate, a compound having a specific ethylenically unsaturated double bond, a compound having a hydroxyl group-containing ethylenically unsaturated double bond, and photopolymerization. A photocurable adhesive composition comprising an initiator has been proposed. Patent Document 1 describes that it has good heat resistance and durability even in bonding members having different linear expansion coefficients.

Generally, a glass screen is used for displays such as CRT, PDP, and PTV, and the glass screen is bonded to a resin frame or body using an adhesive.
Moreover, the solar cell module used for a solar power generation system affixes the protective sheet made from resin on the glass substrate which arranged and wired the photovoltaic cell, and used the adhesive for the side surface. It is manufactured by joining frames such as aluminum.
The photocurable adhesive composition described in Patent Document 1 is said to have good heat resistance and durability even when used in the production of the various displays described above.

JP 2000-63767 A

However, the resin component of the photocurable adhesive composition described in Patent Document 1 has a urethane main chain that is generally considered to have poor weather resistance. Therefore, the photocurable adhesive composition described in Patent Document 1 is used, for example, in the production of the solar cell module described above, and there is a possibility that the adhesiveness may be lowered when exposed to light or heat for a long time. There was room for improving durability.
Therefore, an object of the present invention is to provide an optical device adhesive composition having excellent heat resistance and durability even in bonding members having different linear expansion coefficients.
Here, the “optical device” in the present specification has two or more members, at least one of the members actively or passively transmits light, and the members are joined. It means a light transmissive composite member and a device, equipment, etc. having the light transmissive composite member. “Actively transmitting light” means that the optical device has a light emitter, and the member transmits light from the light emitter and emits light to the outside. “Transmitting” means that the light from the external environment is transmitted by the member and taken into the optical device.

  Another object of the present invention is to provide an optical device having excellent heat resistance and durability.

As a result of intensive studies by the inventor, by using a mixture of an acrylic polymer having a hydrolyzable silicon-containing group and a silane coupling agent, adhesion of members having different linear expansion coefficients can be achieved for a long time. The present invention has been completed by finding that it has excellent heat resistance and durability even when exposed to light and heat.
That is, the present invention provides the following (1) to (4).

(1) a polymer (A) having a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and having at least one hydrolyzable silicon-containing group per molecule;
The adhesive composition for optical devices containing a silane coupling agent (B).

  (2) The adhesive composition for optical devices according to (1), further containing a tin catalyst and / or a titanium catalyst (C).

(3) An optical device having two or more members,
The linear expansion coefficient of the member is different,
An optical device in which the member is bonded with the adhesive composition for optical devices according to (1) or (2).

  (4) The optical device according to (3), wherein at least one of the members having different linear expansion coefficients is a member that transmits light.

The adhesive composition for optical devices of the present invention has excellent heat resistance and durability even in bonding members having different linear expansion coefficients.
The optical device of the present invention has excellent heat resistance and durability.

Hereinafter, the present invention will be described in detail.
The present invention provides a polymer (A) in which the main chain contains an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and has at least one hydrolyzable silicon-containing group per molecule (hereinafter referred to as “a”). , "Polymer (A)") and a silane coupling agent (B) adhesive composition for optical devices (hereinafter also referred to as "the composition of the present invention").

First, the polymer (A) will be described.
The polymer (A) used in the present invention has a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit, and at least one hydrolyzable silicon-containing group per molecule. It is a polymer having. Since the polymer (A) is moisture curable and can be cured at room temperature, the composition of the present invention can be used for adhesion of heat-sensitive plastics and the like. Moreover, a polymer (A) is excellent in the weather resistance, heat resistance, and the adhesiveness with respect to various members. Furthermore, it has excellent oil resistance and high transparency. In particular, a polymer having an acrylic main chain synthesized by living radical polymerization described later has high weather resistance and heat resistance among acrylic polymers, and has low viscosity and excellent workability (handleability).
Therefore, the composition of the present invention has excellent heat resistance and durability even in bonding members having different linear expansion coefficients. Furthermore, it is excellent in oil resistance and the cured product has high transparency.

Examples of the acrylic acid alkyl ester monomer unit include, for example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, and acrylic acid-n. -Hexyl, heptyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate, Biphenyl acrylate is mentioned.
Examples of the methacrylic acid ester monomer unit include, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, methacrylic acid-n-butyl, methacrylic acid isobutyl, methacrylic acid-tert-butyl, methacrylic acid- n-hexyl, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate And biphenyl methacrylate.
These may be used alone or in combination of two or more.

  The main chain of the polymer (A) is not particularly limited as long as it contains an acrylic acid alkyl ester monomer unit and / or a methacrylic acid alkyl ester monomer unit, but the proportion of these monomer units is 50. It is preferable to exceed mass%, and it is more preferable that it is 70 mass% or more.

The main chain of the polymer (A) may contain, in addition to the acrylic acid alkyl ester monomer unit and / or the methacrylic acid alkyl ester monomer unit, a monomer unit copolymerizable therewith. . For example, a monomer unit containing a carboxy group such as acrylic acid or methacrylic acid; a monomer unit containing an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, or N-methylolmethacrylamide; glycidyl acrylate, glycidyl Monomer units containing epoxy groups such as methacrylate; monomer units containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; polyoxyethylene acrylate, polyoxyethylene methacrylate, etc. are moisture A copolymerization effect can be expected in terms of curability and internal curability.
In addition, monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like can be mentioned.

The monomer composition of the polymer (A) is appropriately selected depending on the application and purpose.
For example, when the alkyl chain of the alkyl ester part of the monomer is long, the glass transition temperature is low, and the physical properties of the cured product are soft rubbery elastic bodies. On the other hand, when it is short, the glass transition temperature becomes high and the physical properties of the cured product become hard.
On the other hand, the physical properties after curing largely depend on the molecular weight of the polymer.
Therefore, the monomer composition of the polymer may be appropriately selected according to the desired viscosity, physical properties after curing, and the like, taking into consideration the molecular weight.

The main chain of the polymer (A) can be obtained by a controlled vinyl polymerization method or the like. For example, it can be obtained by performing a solution polymerization method, a bulk polymerization method or the like by a chain transfer agent method, a living radical polymerization method or the like, but is not particularly limited to these methods.
In the chain transfer agent method, a polymer having a functional group at the terminal is obtained by performing polymerization using a chain transfer agent having a specific functional group.
In the living radical polymerization method, a polymer having a molecular weight substantially as designed is obtained by growing the polymerization growth terminal without causing a termination reaction or the like.
The chain transfer agent method is a free radical polymerization and thus has a wide molecular weight distribution and only a polymer having a high viscosity can be obtained. However, the living radical polymerization method has a narrow molecular weight distribution (Mw / Mn is 1) because a termination reaction is unlikely to occur. About 1.5 to 1.5), a polymer having a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. In the present invention, the method described in JP-A-2003-313397 is preferably used.
The reaction is usually carried out by mixing the above-mentioned monomer units, radical initiator, chain transfer agent, solvent and the like and reacting them at 50 to 150 ° C.

Examples of the radical initiator include azobisisobutyronitrile and benzoyl peroxide.
Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, and halogen-containing compounds.
Suitable examples of the solvent include non-reactive solvents such as ethers, hydrocarbons and esters.

  The hydrolyzable silicon-containing group has 1 to 3 hydroxy groups and / or hydrolyzable groups bonded to silicon atoms, and in the presence of moisture or a crosslinking agent, a catalyst or the like is used as necessary. It is a silicon-containing group that can be crosslinked by causing a condensation reaction to form a siloxane bond. Examples thereof include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.

Among these, an alkoxysilyl group is preferable because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.

  The number of hydrolyzable silicon-containing groups possessed by the polymer (A) is at least one per molecule. Further, the bonding position of the hydrolyzable silicon-containing group is preferably at the end of the main chain, and more preferably only at the end of the main chain. Moreover, it is preferable to have a hydrolyzable silyl group at both ends of the main chain from the viewpoints of adhesion to various members, coexistence of adhesive strength and high elongation, and excellent heat resistance.

The method for introducing a hydrolyzable silicon-containing group into the main chain of the polymer (A) is not particularly limited. For example, (i) in the presence of a mercaptan containing a hydrolyzable silicon-containing group as a chain transfer agent, (Ii) a compound having a mercapto group and a reactive functional group other than the hydrolyzable silicon-containing group as a chain transfer agent (for example, a method of polymerizing monomer units and introducing a hydrolyzable silicon-containing group at the molecular end (for example, In the presence of acrylic acid, the monomer unit is polymerized, and the resulting copolymer is a compound having a hydrolyzable silicon-containing group and a functional group capable of reacting with a Y group (for example, an isocyanate group and -Si). (OCH ₃₎ a method of introducing a hydrolyzable silicon-containing group to the compound) is reacted with molecular end and a ₃ group, compounds containing (iii) a hydrolyzable silicon-containing group (e.g., Azobisunitori Compound, disulfide compound) as an initiator to polymerize the monomer unit to introduce a hydrolyzable silicon-containing group at the molecular end, (iv) to polymerize the monomer unit by a living radical polymerization method A method of introducing a hydrolyzable silicon-containing group at the terminal, (v) a compound having a polymerizable unsaturated bond and a hydrolyzable silicon-containing group and the monomer unit, wherein one molecule of hydrolyzable silicon-containing group A method of copolymerizing by selecting polymerization conditions such as the use ratio of monomer units, the amount of chain transfer agent, the amount of radical initiator, the polymerization temperature, etc. so that at least one is introduced per unit can be mentioned.

  Among these, it is preferable that the polymer (A) is produced by adding hydrosilane having a hydrolyzable silicon-containing group to a (meth) acrylic polymer having an alkenyl group at the terminal by hydrosilylation. One.

The (meth) acrylic polymer having an alkenyl group at the end includes, for example, an organic halogen compound or a sulfonyl halide compound as an initiator and a catalyst as the group 8, 9, 10, or 11 of the periodic table. It can be produced by converting a terminal halogen group of a (meth) acrylic polymer obtained by polymerization using a metal complex having a group element as a central metal to an alkenyl group.
Here, a (meth) acrylic polymer having a halogen group at a terminal is conventionally polymerized using a halogen compound such as carbon tetrachloride, carbon tetrabromide, methylene chloride, methylene bromide as a chain transfer agent. Has been manufactured by.
However, with this method, it has been difficult to reliably introduce halogen to both ends of the polymer.

In contrast, JP-A-1-247403 discloses a method for producing an acrylic polymer having an alkenyl group at both ends by using dithiocarbamate or diallyl disulfide having an alkenyl group as a chain transfer agent. Has been described. Japanese Patent Application Laid-Open No. Hei 6-221922 discloses that an acrylic polymer having a hydroxyl group at the terminal is produced using a hydroxyl group-containing polysulfide or an alcohol compound as a chain transfer agent, and alkenyl at the terminal using a hydroxyl group reaction. A method for producing an acrylic polymer having a group is described.
However, in these methods, it is usually difficult to reliably introduce an alkenyl group at the end of the polymer.

On the other hand, as a method for obtaining a (meth) acrylic polymer having a hydrolyzable silicon-containing group without passing through an alkenyl group, Japanese Patent Publication No. 3-14068 discloses a (meth) acrylic monomer containing hydrolyzable silicon. A method of polymerizing in the presence of a radical polymerization initiator having a group-containing mercaptan, a hydrolyzable silicon-containing group-containing disulfide and a hydrolyzable silicon-containing group is described. Japanese Patent Publication No. 4-55444 discloses a method of polymerizing an acrylic monomer in the presence of a hydrolyzable silicon-containing group-containing hydrosilane compound or a tetrahalosilane compound. Further, in JP-A-5-97921, an acrylic monomer is anionically polymerized using a stable carbanion having a hydrolyzable silicon-containing group as an initiator, and the terminal of the polymerization is reacted with a bifunctional electrophilic compound. Describes a method for producing an acrylic polymer having a hydrolyzable silicon-containing group.
However, these methods have problems such as introduction of a functional group into the side chain. That is, it was difficult to reliably introduce a hydrolyzable silicon-containing group at the terminal. In addition, the polymers obtained by these radical polymerizations have a problem that the molecular weight distribution is wide and the viscosity is high.

Therefore, in recent years, living radical polymerization has attracted attention as a method for reliably introducing a functional group to the terminal of an acrylic polymer. Living radical polymerization is described in JP-A-9-272714.
In particular, JP 2000-154205 A and JP 2000-178456 A detail the atom transfer radical polymerization method among the living radical polymerization methods. Here, an organic halide or a sulfonyl halide compound having a particularly highly reactive carbon-halogen bond is used as the initiator, and a periodic table, group 8, group 9, group 10 or group 11 is used as the catalyst. A metal complex having the above metal as a central metal is used. Further, in order to obtain a (meth) acrylic polymer having a functional group at the terminal, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator.

  Japanese Patent Application Laid-Open No. 2003-96106 discloses radical polymerization of (meth) acrylic acid ester monomers using 2,2′-azobis (dimethylvaleronitrile) as an initiator and n as a chain transfer agent. -Dodecyl mercaptan, tert-dodecyl mercaptan and the like are described. Here, when 2-propanol, isobutanol or the like is used as a polymerization solvent, since it has a hydrogen atom bonded to a tertiary carbon atom, it also acts as a chain transfer agent, reducing the amount of chain transfer agent used. It is described as being useful because it is preferable in terms of being able to do so and the molecular weight distribution can be controlled narrower than in the case of using an aromatic solvent.

  The polymer (A) produced from the (meth) acrylic polymer obtained by any polymerization method as described above has a molecular weight distribution of (meth) acrylic polymer obtained by ordinary radical polymerization. While it is usually 2.0 or more, it is very narrow as 1.5 or less, so it has a low viscosity. Also, the functional group introduction rate at the terminal is extremely high.

  The molecular weight of the polymer (A) is not particularly limited, but the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) is 500 to 100,000, the degree of difficulty during polymerization, compatibility, It is preferable in terms of handling viscosity. Among them, those having a number average molecular weight of 1,000 to 50,000 are preferable from the viewpoint of balance between strength and viscosity, and those having a number average molecular weight of 2,000 to 30,000 are points such as ease of handling such as workability and adhesiveness. And more preferable.

  A polymer (A) is used individually or in mixture of 2 or more types.

  A well-known thing can be used as a polymer (A). Specific examples include SMAP (Kaneka Telechelic Polyacrylate) SA100S, SA110S, SA120S and SA200SX manufactured by Kaneka Chemical Co., Ltd. and Kaneka MS Polymer S943 manufactured by Kaneka Chemical Co., Ltd.

Next, the silane coupling agent (B) will be described.
The silane coupling agent used in the present invention is not particularly limited, and examples thereof include an epoxy group, an amino group (ureido group), a mercapto group, a (poly) sulfide group, a vinyl group, a methacryloxy group, a carboxy group, an isocyanate group, and a ketimine. And a silane coupling agent having at least one organic functional group selected from the group consisting of a group, a halogen, and a cyclopropyl group. By containing the silane coupling agent, the composition of the present invention can improve adhesion to various members including glass, and as a result, adhesion of members having different linear expansion coefficients due to the polymer (A). The heat resistance and durability can be further improved.

  More specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Epoxy group-containing silane compounds such as methoxysilane and γ-glycidoxypropylmethyldiethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyl Diethoxysilane, γ-ureidopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ -Aminopropyltriethoxy Amino group-containing silane compounds such as silane and N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyl Mercapto group-containing silane compounds such as diethoxysilane; (poly) sulfide group-containing silane compounds such as bis (triethoxysilylpropyl) tetrasulfide and bis (triethoxysilylpropyl) disulfide; vinyltrichlorosilane, vinyltrimethoxysilane, vinyl Vinyl group-containing silane compounds such as triethoxysilane and vinyltris (β-methoxyethoxy) silane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxy Silane, .gamma.-methacryloxypropyl methyl diethoxy silane, .gamma.-methacryloxypropyl methacryloxy group-containing silane compounds such as triethoxy silane;

  Carboxysilane compounds such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; Trimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatoethyltrimethoxysilane, γ-isocyanateethyltriethoxysilane, γ-isocyanateethylmethyl Isocyanate group-containing silane compounds such as diethoxysilane and γ-isocyanatoethylmethyldimethoxysilane; N- (1,3-dimethylbutylidene) -3- (trimethoxy) Silyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxy) Silyl) -1-propanamine, ketimine group-containing silane compounds such as N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine; γ-chloropropyltrimethoxysilane and the like; Halogen-containing silane compounds; silyl esters such as methyl silyl esters; silane compounds such as orthosilicate esters and the like. These may be used alone or in combination of two or more. Moreover, you may use the reaction material of these, an epoxy resin, or polyisocyanate.

  Among these, amino group-containing silane compounds, epoxy group-containing silane compounds, and vinyl group-containing silane compounds are preferably used because they are excellent in adhesiveness to various members.

  A commercial item may be used for the said silane coupling agent, and you may manufacture it. Manufacturing conditions are not particularly limited, and can be performed by known methods and conditions.

  It is preferable that 1-100 mass parts of silane coupling agents are contained with respect to 100 mass parts of the polymer (A). If it is this range, adhesiveness can be improved, without having a bad influence on the physical property of hardened | cured material. From the point which is excellent by this characteristic, 1-50 mass parts is more preferable, and, as for content of a silane coupling agent, 1-20 mass parts is still more preferable.

The composition of the present invention preferably contains a tin catalyst and / or a titanium catalyst. By containing these catalysts, it is possible to promote the progress of the curing reaction and shorten the work time to reach the curing, thereby shortening the tack-free time, which is excellent in practical use.
A conventionally well-known thing can be used for a tin catalyst and / or a titanium catalyst.
Examples of the tin catalyst include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; reaction products of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate.
Examples of the titanium catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate.
These may be used alone or in combination of two or more.

  The content of the tin catalyst and / or the titanium catalyst is sufficient in that the action of the catalyst can be fully exerted, there is no problem with compatibility with other components, and local heat generation and foaming do not occur during curing. 0.1 to 20 parts by mass is preferable. 0.5-15 mass parts is preferable at the point which is excellent by this characteristic, and 0.5-10 mass parts is still more preferable.

The composition of the present invention can contain various additives as long as the effects of the present invention are not impaired.
Although the kind of additive is not particularly limited, additives generally used in moisture curable compositions or reaction curable compositions such as fillers (reinforcing materials), plasticizers, anti-aging agents, colorants, Examples include thixotropic agents, adhesion-imparting agents, physical property modifiers, antioxidants, ultraviolet absorbers, flame retardants, and other known additives.

  The composition of this invention can be manufactured by a well-known method. For example, in a nitrogen atmosphere, the polymer (A), the silane coupling agent (B), and optionally the tin catalyst and / or titanium catalyst (C), and other additives are added using a stirrer. It can be obtained by mixing and dispersing.

The composition of the present invention is a moisture curable type and can be used as a one-component curable composition. Further, if necessary, the polymer (A) and the silane coupling agent (B) can be used as a two-component type with the main agent side and the tin catalyst and / or titanium catalyst (C) as the curing agent side. .
When the composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the hydrolyzable silicon-containing group. In addition, the curing reaction can be advanced by appropriately supplying water.

  The composition of the present invention obtained as described above is composed of a polymer (A) excellent in weather resistance, heat resistance and adhesion to various members, and a silane coupling agent that imparts adhesion to various members ( By mixing and using B), it has excellent heat resistance and durability even in bonding members having different linear expansion coefficients.

The kind of the member bonded using the composition of the present invention is not particularly limited, such as glass, resin and metal.
Examples of the resin include acrylic, polycarbonate, polyester, polyurethane, silicone, polypropylene, polyphenylene terephthalate, polybutylene terephthalate, and polyvinyl chloride. Among these, acrylic, polyvinyl chloride, and polycarbonate are preferable because they are excellent in adhesion to the composition of the present invention.
Examples of the metal include aluminum, stainless steel, electrodeposition coated steel, soft iron steel, brass steel, carbon steel, titanium, lead, vinyl chloride steel, and aluminum magnesium steel. Among these, aluminum, vinyl chloride steel, and electrodeposition coated steel are preferable in terms of excellent adhesion to the composition of the present invention.

  The composition of the present invention may be used for bonding the same material or may be used for bonding different materials. As described above, the composition of the present invention has excellent heat resistance and durability even in bonding members having different linear expansion coefficients. Therefore, it is suitably used for the optical device of the present invention described later.

Therefore, the composition of the present invention is used as an adhesive composition for optical devices by taking advantage of the excellent characteristics as described above.
Specifically, for example, solar cell module, CRT, plasma display, projection television, liquid crystal display (LCD), light emitting diode (LED) display, EL film display, LED traffic light, camera, microscope, telescope, optical disk, optical fiber, scanner , Laser beam printers, digital copiers, projection lights, facsimiles, electric bulletin boards, projectors, and vehicular lamps.
In particular, it is suitably used for bonding a member (for example, a screen portion) including a glass substrate used for a CRT, a plasma display, a projection television, or the like to a member (for example, a resin frame) made of a material other than glass.
Moreover, the composition of this invention is used suitably also for manufacture of a solar cell module and the panel for condensing. Furthermore, it is suitably used for bonding a cover or a lens used for a vehicular lamp to a lamp housing.

Next, the optical device of the present invention will be described.
The optical device of the present invention is an optical device having two or more members, the members have different linear expansion coefficients, and the members are bonded with the above-described adhesive composition for optical devices of the present invention. . Conventional optical devices have problems in heat resistance and durability because members having different linear expansion coefficients are bonded to each other by conventional adhesive compositions. On the other hand, as described above, the optical device of the present invention is bonded with the optical device adhesive composition of the present invention having excellent heat resistance and durability even in the bonding of members having different linear expansion coefficients. Excellent heat resistance and durability. Therefore, the optical device of the present invention is excellent in heat resistance and durability even when exposed to light or heat for a long time.

Specific examples of the optical device of the present invention include the optical devices described above.
In the optical device of the present invention, it is preferable that at least one of the members having different linear expansion coefficients is a member that transmits light. Specifically, as the optical device of the present invention, for example, a member including a glass substrate (for example, a screen portion) and a member made of a material other than glass (for example, a resin frame) are used for the optical device of the present invention. Preferable examples include displays such as CRTs, plasma displays, and projection televisions bonded with an adhesive composition. A solar cell module in which members having different linear expansion coefficients (for example, a glass substrate and a protective sheet made of resin) are bonded with the adhesive composition for optical devices of the present invention is also preferable. Furthermore, a vehicle lamp in which a cover or lens used for a vehicle lamp and a lamp housing are bonded with the adhesive composition for optical devices of the present invention is also preferable.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
(Examples 1-2)
The components shown in Table 1 below were mixed using the stirrer at the composition (parts by mass) shown in Table 1 to obtain the compositions of Examples 1 and 2.
About each composition immediately after obtained, the viscosity was measured using the E-type viscosity meter.
Next, the composition of Example 1 or 2 between a soda lime glass plate (50 mm square, thickness 1 mm) and an acrylic plate (50 mm square, thickness 2 mm) arranged to face the soda lime glass plate. A test specimen was obtained by placing an object and leaving it for 14 days in an environment of 23 ° C. and 50% RH.
Using this test body, heat resistance and cold heat resistance were evaluated as follows.
The results are shown in Table 1.

(Heat resistance test)
The state of the adhesion surface after putting the obtained test body into an 80 degreeC oven for 500 hours was observed visually.
In Table 1, “◯” indicates that there is no peeling, and “×” indicates a state where most of the peeling occurs.

(Cool resistance test)
The obtained specimen was cooled to −40 ° C. and maintained for 30 minutes, then heated to 85 ° C. over 1 hour, maintained at 85 ° C. for 30 minutes, and then cooled to −40 ° C. over 1 hour. . This was regarded as one cycle, and the state of the adhesion surface after repeating 100 cycles was visually observed.
In Table 1, “◯” indicates that there is no peeling, and “×” indicates a state where most of the peeling occurs.

The components shown in Table 1 are as follows.
-Polymer (A): SMAP SA100S, manufactured by Kaneka Chemical Co., Ltd.-Silane coupling agent 1: γ-aminopropyltriethoxysilane, A-1100, manufactured by Nihon Unicar Co., Ltd.-Silane coupling agent 2: γ-glycid Xylpropyltrimethoxysilane, A-187, manufactured by Nihon Unicar Co., Ltd. ・ Silane coupling agent 3: vinyltrimethoxysilane, A-171, manufactured by Nihon Unicar Co., Ltd. ・ Tin catalyst: dibutyltin diacetylacetonate, U-220, Nitto Kasei Co., Ltd. Made

(Comparative Examples 1-2)
The components shown in Table 2 below were mixed using the stirrer at the composition (parts by mass) shown in Table 2 to obtain compositions of Comparative Examples 1 and 2.
About each composition immediately after obtained, the viscosity was measured using the E-type viscosity meter.
Next, the composition of Comparative Example 1 or 2 between a soda lime glass plate (50 mm square, 1 mm thickness) and an acrylic plate (50 mm square, 2 mm thickness) disposed to face the soda lime glass plate. An object was placed and cured by applying energy of 2000 mJ / cm ² using a high-pressure mercury lamp to obtain a test specimen.
Using this test body, the heat resistance and the cold resistance were evaluated in the same manner as described above.
The results are shown in Table 2.

The components shown in Table 2 are as follows.
-Urethane acrylate 1: Art resin UN9200A, manufactured by Negami Kogyo Co., Ltd.-Urethane acrylate 2: Aronix M1310, manufactured by Toagosei Co., Ltd.-HEMA: 2-hydroxyethyl methacrylate, manufactured by Mitsubishi Gas Chemical Co., Ltd.-TPO: 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, manufactured by BASF

  As is clear from the results shown in Tables 1 and 2 above, the compositions of Examples 1 and 2 have the same viscosity as the conventional photocurable adhesive compositions (Comparative Examples 1 and 2). However, the heat resistance and cold resistance were remarkably excellent.

(Example 3)
A manufacturing example of the solar cell module will be described with reference to the drawings.
FIG. 1 is a schematic view showing a manufacturing process of a solar cell module.
As shown in FIG. 1, solar cells 3 were arranged on the front glass 1 and connected by wiring 5.
Next, the adhesive composition 7 for optical devices of this invention was apply | coated to the circumference | surroundings of the photovoltaic cell 3 arranged on the front glass 1, and it was made to adhere | attach with the resinous back surface protection sheet 9. FIG.
Next, the adhesive composition 7 for optical devices of this invention is apply | coated to the side part of what adhere | attached the front glass 1, the photovoltaic cell 3, and the back surface protection sheet 9, the aluminum frame 11 is adhere | attached, and a solar cell module 13 was produced.
About the obtained solar cell module 13, heat resistance and cold-heat resistance were evaluated similarly to the above-mentioned method. The results were all “◯ (no peeling)”.

FIG. 1 is a schematic view showing a manufacturing process of a solar cell module.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Front glass 3 Solar cell 5 Wiring 7 Adhesive composition for optical devices of this invention 9 Back surface protection sheet 11 Aluminum frame 13 Solar cell module

Claims (4)

A polymer (A) having a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and having at least one hydrolyzable silicon-containing group per molecule;
The adhesive composition for optical devices containing a silane coupling agent (B).   Furthermore, the adhesive composition for optical devices of Claim 1 containing a tin catalyst and / or a titanium catalyst (C). An optical device having two or more members,
The linear expansion coefficient of the member is different,
An optical device in which the member is bonded with the adhesive composition for optical devices according to claim 1.   The optical device according to claim 3, wherein at least one of the members having different linear expansion coefficients is a member that transmits light.

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