JP2018055028A - Optical member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical member comprising a plurality of light transmissive members that are capable of bonding to each other by covalent bond via molecular adhesive with high bond strength without using viscous adhesive, do not cause detachment, achieve precise dimensional accuracy, exhibit high optical transparency without yellow discoloration and deterioration, and can maintain high optical transparency even after long term use.SOLUTION: An optical member 1 includes a first light transmissive member 10 formed of addition crosslinking silicone and a second light transmissive member 20 formed of polycarbonate and the like. The surface of at least one of the light transmissive members includes, on a modification portion surface-modified by reactive functional group-containing alkoxy siloxane containing a functional group coupled to a surface exposure reactive group of the surface, an amplification portion amplified by plural vinyl groups-containing alkoxy siloxane. This structure bonds the surface of the one of the light transmissive members to the surface of the other thereof with the amplifier portion interposed therebetween.SELECTED DRAWING: Figure 1

Description

  In the present invention, a light-transmitting member made of addition-crosslinking type silicone and a light-transmitting member of the same kind or different kinds are bonded by a covalent bond via a molecular adhesive molecule without using a viscous adhesive. The present invention relates to an optical member having high light transmittance.

  Low surface tension of silicone that is difficult to adhere and adhere to light-transmitting members molded with silicone and light-transmitting members molded with different kinds of cross-linked rubber, resin, metal, ceramics or glass, or silicone other than silicone Due to the reasons described above and because the physicochemical properties are significantly different, simply contacting or adhering with a viscous adhesive does not result in strong bonding.

  Furthermore, when these light-transmitting members are bonded with a viscous adhesive, the adhesive force is very weak because of the intermolecular force between the viscous adhesive molecules. If the material of the light transmissive member is changed, an optimum viscous adhesive must be selected by trial and error, which takes a lot of trouble.

  In the adhesion using such a viscous adhesive, the viscous adhesive protrudes from the end portion of the light transmissive member to be bonded, or it is difficult to strictly control the thickness of the viscous adhesive layer. Because of such a problem, undesired irregular reflection or refraction of an optical member using a light-transmitting member is caused. Therefore, when manufacturing an optical member that requires precision, fatal defective products of the optical member are frequently produced, resulting in a decrease in yield. Moreover, it is difficult to homogenize the adhesion of light transmissive members from lot to lot. The defect rate and productivity depend on the experience and ability of the person in charge of production, producing high-quality products in high yields and in large quantities. Can not do it.

  In addition, these light-transmitting members bonded with a viscous adhesive cause a decrease in permeability due to uneven curing of the viscous adhesive component and residual air, or viscous bonding due to a large amount of light or heat generated by high-intensity light-emitting diodes, etc. It causes yellowing of the agent, resulting in a reduction from the original high transmittance of the highly transparent light transmissive member.

  A composite optical element manufactured without using an adhesive is described in Patent Document 1. This composite optical element is obtained by laminating a cured product of an optical resin composition containing N-acryloylcarbazole, a polyfunctional polyester acrylate, and dimethylol tricyclodecanediacrylate on the surface of an optical substrate.

  When the optical resin composition is heated to high molecular weight or vulcanized on an optical substrate and cured, sufficient dimensional accuracy is obtained due to thermal expansion and steric contraction during heating and curing. There is a risk that it will not be able to be joined, or it will not be fully bonded and may cause peeling.

JP 2008-158361 A

  The present invention has been made to solve the above-described problems, and a plurality of light-transmitting members are bonded with high bonding strength by covalent bonding via molecular adhesives without using viscous adhesives. It is an object to provide an optical member that does not cause peeling, exhibits precise dimensional accuracy, exhibits high light transmittance without causing yellowing or deterioration, and can maintain high light transmittance even after long-term use. To do.

  The optical member according to the claims made to achieve the above object includes a first light transmissive member formed of addition-crosslinking type silicone, polycarbonate, cycloolefin polymer, (meth) acrylic resin, The surface of at least one of the light transmissive member and the second light transmissive member formed of any one selected from silicone and glass is unsaturated group, epoxy group, ureido bonded to the surface exposed reactive group therein A modified site surface-modified with a reactive functional group-containing alkoxysiloxane containing a functional group selected from a group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl groups, an amino group, a nitrile group, and an azide group By having an amplification site amplified by a plurality of vinyl group-containing alkoxysiloxanes, On the surface of the square of the light transmission member, it is that are joined.

  In the optical member, the first light transmissive member and the second light transmissive member include the surface modification and the amplification by the reactive functional group-containing alkoxysiloxane and the reactive functional group-containing alkoxysiloxane. It is preferable that it is joined by.

  In the optical member, the first light-transmitting member and the second light-transmitting member include the reactive functional group-containing alkoxysiloxane and the plurality of the reactive functional group-containing alkoxysiloxane on the surface on the bonding side of each other. It may be bonded via a covalent bond of vinyl group-containing alkoxysiloxane.

In the optical member, the vinyl group-containing alkoxysiloxane is represented by the following chemical formula, for example.
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
(Wherein n is a number from ¹ to 20, R ¹ is C _a H _{2a + 1} , a is a number from 1 to 3, and R ² and R ³ are CH ₃ or CH ₂ = CH) More specifically, n is a number of 1 to 5, a is a number of 1 to 3, R ² is CH ₃ , and R ³ is a vinyl-containing silane coupling agent such as CH ₂ = CH. That's it.

  In the optical member, the reactive functional group-containing alkoxysiloxane may be a silane coupling agent.

  In the optical member, the reactive functional group-containing alkoxysiloxane is, for example, an amino group and an alkoxy group-containing silane compound; a vinyl group and an alkoxy group-containing silane compound; an epoxy group and an alkoxy group-containing silane compound, a styryl group and an alkoxy group-containing silane compound. ; (Meth) acrylic group and alkoxy group-containing silane compound; ureido group and alkoxy-containing silane compound; mercapto group and alkoxy-containing silane compound; sulfide group and alkoxy-containing silane compound; isocyanate group and alkoxy-containing silane compound, allyl group and alkoxy-containing Silane compound; alkyl group and alkoxy group-containing silane compound; aryl group and alkoxy group-containing silane compound; alkyl group and chlorosilane group-containing silane compound; tetraalkoxysilane compound Is that that.

  In the optical member, the reactive functional group-containing alkoxysiloxane is preferably the amino group and alkoxy group-containing silane compound which is aminoalkyltrialkoxysiloxane or aminoalkylaminoalkyltrialkoxysiloxane.

In the optical member, the aminoalkylaminoalkyltrialkoxysiloxane has the following chemical formula:
H ₂ N- (C _p H _2p ) -NH- (C _q H _2q ) -Si (-OC _r H _{2r + 1} ) ₃
(Wherein, p, q, and r are each independently a number of 1 to 6).

  The optical member is, for example, at least one of an exposed surface of the first light transmissive member, a surface of the modified portion thereof, and a surface of the amplification portion thereof, and / or the exposure of the second light transmissive member. At least one of the surface, the surface of the modified portion thereof, and the surface of the amplification portion thereof is a corona discharge treatment surface, a plasma treatment surface, an ultraviolet treatment surface, and / or an excimer treatment surface.

  The optical member has, for example, a surface on the joining side of the first light transmissive member and the second light transmissive member, on the one hand, the modified portion and the amplification portion, Silanepropyltriethoxysilane compound treated surface, titanate compound treated surface, aluminate compound treated surface, thiol compound treated surface, azide compound treated surface, corona discharge treated surface, plasma treated surface, UV treated surface, and / or excimer treated surface It is what.

  In the optical member, the second light transmissive member includes a plate-like support, a sealing material enclosing the light emitting element, a package molded body surrounding the light emitting element, and a streaky flow path for flowing a liquid specimen. It may be any one selected from the formed base sheet.

  In the optical member, it is preferable that at least a part of the first light transmitting member is a lens.

  The optical member has, for example, the transmittance when the first light transmissive member and the second light transmissive member are joined, and the transmittance is the first light transmissive member and the second light transmissive member. When the two are bonded together, the transmittance and the difference are preferably 5% at the maximum, for example, 5 to 0%, more preferably 3 to 0%.

  The manufacturing method of the optical member made to achieve the above object includes a first light transmissive member formed of metal, polymer resin, crosslinked rubber, glass or ceramics, and metal, polymer resin, crosslinked rubber. The surface of at least one of the light transmissive member and the second light transmissive member formed of glass or ceramics is unsaturated group, epoxy group, ureido group, mercapto group, sulfide group, isocyanate group, a plurality of alkoxy By treating with a reactive functional group-containing alkoxysiloxane containing a functional group selected from a silyl group, an amino group, a nitrile group and an azide group and a plurality of vinyl group-containing alkoxysiloxanes, the first light-transmissive member and the first Reactive functional group-containing alkoxy on the surface-exposed reactive group on the surface of the joining side of at least one light transmissive member with the second light transmissive member Reacting with oxane to form a modified site by surface modification, and amplifying the modified site with the plural vinyl group-containing alkoxysiloxane to form an amplified site; and Bonding the surfaces on the bonding side to obtain an optical member.

  In the optical member of the present invention, a first light-transmitting member made of addition-crosslinking silicone such as an addition-crosslinking type silicone resin or silicone rubber and a second light-transmitting member of the same kind or different kinds are viscously bonded. Without using an agent, bonding is performed with high bonding strength by a covalent bond directly via a molecular adhesive which is a reactive functional group-containing alkoxysiloxane and a plurality of vinyl group-containing alkoxysiloxanes. The covalent bonding by the molecular adhesive is firmly bonded by the covalent bonding by the molecular adhesive even if it is a light-transmitting member made of a material that is difficult to bond originally, such as silicone. Does not occur. In addition, the optical member is thinly bonded between the photocurable members via a molecular adhesive without depending on the adhesive adhesive, so that the adhesive protrudes from the bonding surface or the adhesive layer. There is no fear of peeling. Therefore, the optical member does not cause undesired irregular reflection or refraction.

  In this optical member, a reactive functional group-containing alkoxysiloxane and a plurality of vinyl group-containing alkoxysiloxanes react sequentially on the surface of the light-transmitting member, and the modified portion is surface-modified by the reactive functional group-containing alkoxysiloxane. Each of the modified sites is formed with an amplification site amplified by a plurality of vinyl group-containing alkoxysiloxanes, and is bonded with high bonding strength by direct covalent bonding.

  This optical member is a reactive functional group-containing alkoxy that reacts easily with a surface-exposed reactive group exposed on at least one of the bonding side surfaces of the first light-transmissive member and the second light-transmissive member. The siloxane reacts to bond first to form a surface modified surface modification site, and then the modified site contains a plurality of vinyl group-containing alkoxysiloxanes that react and bond to amplify multiple vinyl group amplified sites. And is joined to the surface of the other light-transmitting member via the amplification site.

  This optical member is less likely to cause mechanical or chemical peeling. Further, this optical member has a thin reactive functional group-containing alkoxysiloxane and a plurality of vinyls between the first light-transmitting member and the second light-transmitting member without depending on the fluid curable adhesive. Since, for example, a monomolecular film and a monomolecular film are formed and bonded via the group-containing alkoxysiloxane, there is no fear that they protrude from the bonded surface or peel off from the cured product layer.

  This optical member is much stronger than the bonding by the intermolecular force of the adhesive, rather than the covalent bond between the reactive functional group-containing alkoxysiloxane and the plural vinyl group-containing alkoxysiloxane. The second light transmitting member is joined. It is stable to contact with solutes such as water, especially hot water, and liquid drugs, especially alcohol solutions.

  Since this optical member is obtained by joining light transmissive members that have been polymerized or vulcanized and cured in advance by covalent bonding with a molecular adhesive, thermal expansion between the light transmissive members and There is no need to consider steric contraction, and precise dimensional accuracy can be expressed.

  Furthermore, since this optical member is a thin film such as a monomolecular film and bonded by covalent bonding of molecular adhesive molecules, it retains the light resistance of the light-transmitting member itself, does not cause yellowing or deterioration, and light The original high light transmittance of the transparent member can be maintained. This optical member has a high transmittance of the addition cross-linked silicone of the first light transmissive member and a high transmittance of polycarbonate, cycloolefin polymer, (meth) acrylic resin, silicone, glass, etc. of the second light transmissive member. High permeability can be maintained without sacrificing rate.

It is a side view which shows an example of the optical member to which this invention is applied. It is a side view which shows the example of another optical member to which this invention is applied. It is a side view which shows the example of another optical member to which this invention is applied. It is a perspective view which shows the middle of manufacture of another optical member to which this invention is applied. The first light-transmitting member of silicone and the second light-transmitting member of cycloolefin polymer, each single member and a member bonded together with no treatment and no adhesive, and a molecular adhesive to which the present invention is applied It is a figure which shows each transmittance | permeability of the optical member joined by this, and the optical member adhere | attached with the adhesive adhesive which does not apply this invention.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

The optical member 1 of the present invention will be described with reference to FIG. 1. A bottom surface 10 _{down of} a plate-like first light transmitting member 10 formed of addition-crosslinking silicone, polycarbonate, cycloolefin polymer, (meta ) The upper surface 20 _up of the plate-like second light-transmissive member 20 formed of acrylic resin, silicone, or glass is formed using a reactive functional group-containing alkoxysiloxane and a plurality of vinyl group-containing alkoxysiloxanes. It is joined by a covalent bond.

For example, the lower surface 10 _down of the first light transmissive member 10 is previously subjected to a surface activation treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, or excimer treatment, and the upper surface of the second light transmissive member 20. 20 _up is previously subjected to surface activation treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment or excimer treatment, so that hydroxyl, carboxyl and / or carbonyl groups are formed on the surfaces 10 _down and 20 _up. It is newly generated as a reactive functional group and is scattered and exposed while being amplified.

Thereto, a molecular adhesive is used which is obtained by immersing, coating, spraying, etc. a reactive functional group-containing alkoxysiloxane and a plurality of vinyl group-containing alkoxysiloxanes. By this treatment, first, a reactive functional group containing a functional group selected from an unsaturated group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl groups, an amino group, a nitrile group, and an azide group. The contained alkoxysiloxane is bonded to a surface exposed reactive group such as a hydroxyl group, a carboxyl group or a carbonyl group through a covalent bond such as an ether bond, an ester bond, an amide bond, an imino bond or a urethane bond, and has low reactivity. The surface exposed reactive group is surface-modified with these reactive functional group-containing alkoxysiloxanes having high reactivity, and the alkoxysilyl group derived from the reactive functional group-containing alkoxysiloxane is exposed, for example, forming a monomolecular film, the first lower surface 10 _down the surface of the upper surface 20 _{Stay up-the} second light transmitting member 20 of the light transmitting member 10 It is reformed.

  Next, the alkoxysilyl group of the plural vinyl group-containing alkoxysiloxane reacts with the alkoxysilyl group at the modified site, and is bonded via a new siloxy bond by an alcohol reaction. Then, it is amplified with a plurality of highly reactive vinyl groups derived from a plurality of vinyl group-containing alkoxysiloxanes from one of the surface exposed reactive groups having low reactivity, and forms, for example, a monomolecular film.

As a result, amplification sites are formed in which a plurality of vinyl groups are exposed from the lower surface 10 _down of the first light transmissive member 10 and the upper surface 20 _up of the second light transmissive member 20. If necessary, if the surface where the amplification site is exposed is subjected to corona discharge treatment, plasma treatment, ultraviolet treatment, and / or excimer treatment, at least a part or all of the vinyl group is oxidatively cleaved to expose silanol. It becomes an amplification site where a group or a silyl group is generated.

When the first light transmissive member 10 and the second light transmissive member 20 are simply brought into contact with each other on the lower surface 10 _down and the upper surface 20 _up , or further overlapped under pressure or reduced pressure, The joint surface side of the light transmissive member is joined to the joint surface side of the other light transmissive member via the amplification site via a covalent bond. At this time, the vinyl groups in the amplification sites of the light transmissive members 10 and 20, the silanol groups, the silyl groups, and combinations thereof react with each other.

  In this way, from the surface exposed reactive groups of the light transmissive members 10 and 20, a single molecule reactive functional group-containing alkoxysiloxane that is a molecular adhesive forms a monomolecular film that reacts with another molecule. The single-molecule plural vinyl group-containing alkoxysiloxane, which is an adhesive, reacts to form a monomolecular film, which contributes to the joining of the light transmissive members 10 and 20. Addition reaction of each vinyl group and / or alkoxy by covalent bond through monomolecular film of reactive functional group-containing alkoxysiloxane and monomolecular film of multi-vinyl group-containing alkoxysiloxane which is another molecular adhesive Due to the condensation reaction between the siloxy groups, the two light-transmitting members 10 and 20 are chemically bonded by a covalent bond through a monomolecular film of a molecular adhesive.

The reactive functional group-containing alkoxysiloxane and the plurality of vinyl group-containing alkoxysiloxanes may be used separately in two liquids as a molecular adhesive, or may be used by mixing in one liquid. The use ratio or mixing ratio is preferably 1 to 0.1: 1 by weight. Above all, the mixture
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
Wherein n is a number from ^{1 to} 5, R ¹ is C _a H _{2a + 1} , a is a number from 1 to 3, R ² is CH ₃ , R ³ is CH ₂ = CH, and the like A mixture of a vinyl-containing silane coupling agent and N- (3- (trimethoxysilyl) propyl) ethylenediamine is even more preferable.

  The first light transmissive member 10 is made of addition-crosslinking silicone and is highly transparent.

  The addition crosslinkable silicone forming the first light transmissive member 10 is an addition crosslinkable silicone resin or an addition crosslinkable silicone rubber, and more specifically vinylmethylsiloxane / polydimethylsiloxane synthesized in the presence of a Pt catalyst. Copolymer, vinyl terminated polydimethylsiloxane, vinyl terminated diphenylsiloxane / polydimethylsiloxane copolymer, vinyl terminated diethylsiloxane / polydimethylsiloxane copolymer, vinyl terminated trifluoropropylmethylsiloxane / polydimethylsiloxane copolymer, vinyl terminated polyphenylmethylsiloxane, vinylmethyl Siloxane / dimethylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane / diphenylsiloxane copolymer, trimethylsilo Sun group-terminated dimethylsiloxane / vinylmethylsiloxane / ditrifluoropropylmethylsiloxane copolymer, vinyl group-containing polysiloxane such as trimethylsiloxane group-terminated polyvinylmethylsiloxane, H-terminated polysiloxane, methyl Hsiloxane / dimethylsiloxane copolymer, polymethylHsiloxane, Compositions of H group-containing polysiloxanes exemplified by polyethyl H siloxane, H-terminated polyphenyl (dimethyl H siloxy) siloxane, methyl H siloxane / phenyl methyl siloxane copolymer, methyl H siloxane / octyl methyl siloxane copolymer; aminopropyl terminated polydimethyl Siloxane, aminopropylmethylsiloxane / dimethylsiloxane copolymer, aminoethylaminoisobutylmethylsiloxane Dimethylsiloxane copolymer, aminoethylaminopropylmethoxysiloxane / dimethylsiloxane copolymer, amino group-containing polysiloxane exemplified by dimethylamino-terminated polydimethylsiloxane, and epoxypropyl-terminated polydimethylsiloxane, (epoxycyclohexylethyl) methylsiloxane / dimethylsiloxane copolymer Containing an epoxy group-containing polysiloxane, an acid anhydride group-containing polysiloxane exemplified by succinic anhydride-terminated polydimethylsiloxane, and isocyanate groups such as toluyl diisocyanate and 1,6-hexamethylene diisocyanate It is obtained from a composition with a compound.

  The processing conditions for producing the first light-transmissive member 10 from these addition-crosslinking silicone-forming compositions vary depending on the type and characteristics of the addition reaction, but are not uniquely determined. And heating for 1 minute to 24 hours. Thereby, addition-crosslinking type silicone is obtained as the first light transmitting member. The reaction time is longer when the physical properties of the addition-crosslinking silicone are better under low-temperature processing conditions. When productivity faster than physical properties is required, the processing is performed at a high temperature for a short time. When machining must be performed within a certain period of time depending on the production process and work environment, the machining temperature is set to a relatively high temperature within the above range in accordance with the desired machining time.

Examples of the material forming the second light transmissive member 20 include inorganic materials such as highly transparent resin and glass. More specifically, an amorphous resin such as polyvinyl chloride (PVC); polystyrene (PS); acrylonitrile-butadiene-styrene copolymer (ABS); polyamide (PA); polymethyl methacrylate (PMMA); Polycarbonate (PC); polybutadiene terephthalate (PBT) and polyethylene terephthalate (PET); polyphenylene sulfide (PPS); polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, and silicone (Meth) acrylates and (meth) acrylic resins such as pentaerythritol tetra (meth) acrylate; addition-crosslinking silicones as described above; vinylmethylsilicone (VMQ), methylphenyl Silicones such as ricone (PVMQ), fluoromethyl silicone (FVMQ), and dimethyl silicone (MQ), peroxide cross-linked silicones, condensation cross-linked silicones, silicones exemplified by UV cross-linkable silicones, these silicones and olefins A three-dimensional silicone having a three-dimensional cross-linked structure produced by placing the co-blend of the above in a molding die or the like and cross-linking it;
Inorganic, preferably glass such as quartz, borosilicate glass, and alkali-free glass. In addition, (meth) acrylate means an acrylate and / or a methacrylate.

  When the second light transmissive member 20 is formed of these materials, the light transmissive property is extremely good regardless of whether it is a resin or an inorganic material. If the resin is a crystalline resin, it exhibits an absorptivity at a specific wavelength, so that the light transmittance is insufficient.

The multi-vinyl group-containing alkoxysiloxane is not particularly limited as long as it can amplify the modified site by the reactive functional group-containing alkoxysiloxane, but R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
Wherein n is a number from ¹ to 20, R ¹ is C _a H _{2a + 1} , a is a number from 1 to 3, and R ² and R ³ are CH ₃ or CH ₂ = CH. More specifically, in the formula, n is a number of 1 to 5, a is a number of 1 to ₃ , and a vinyl-containing silane cup represented by R ₂ = CH ₃ , R ₃ = CH ₂ = CH A ring agent is mentioned. In the case of having a vinyl group and a SiH group, the reaction may be promoted with a metal catalyst, for example, a platinum-containing compound, and may be joined.

The reactive functional group-containing alkoxysiloxane is an unsaturated group, epoxy group, ureido group, mercapto group, sulfide group, isocyanate group, multiple alkoxysilyl groups, amino group, nitrile group and / or bonded to the surface exposed reactive group. If it contains an azide group, it will not specifically limit. For example, as reactive functional group-containing alkoxysiloxane,
Vinyl group and alkoxy group-containing silane compounds such as vinyltrimethoxysilane (KBM-1003) and vinyltriethoxysilane (KBE-1003);
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303), 3-glycidoxypropylmethyldimethoxysilane (KBM-402), 3-glycidoxypropyltrimethoxysilane (KBM-403), Epoxy group and alkoxy group-containing silane compounds such as 3-glycidoxypropylmethyldiethoxysilane (KBE-402) and 3-glycidoxypropyltriethoxysilane (KBE-403);
styryl and alkoxy group-containing silane compounds such as p-styryltrimethoxysilane (KBM-1403);
3-methacryloxymethyldiethoxysilane, 3-methacryloxymethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), 3-methacryloxy Contains (meth) acrylic and alkoxy groups such as propylmethyldiethoxysilane (KBE-502), 3-methacryloxypropylmethyldiethoxysilane (KBE-503), 3-acryloxypropyltrimethoxysilane (KBM-5103) Silane compounds;
Ureido group and alkoxy-containing silane compounds such as 3-ureidopropyltriethoxysilane (KBE-585);
Mercapto group and alkoxy-containing silane compounds such as 3-mercaptopropylmethyldimethoxysilane (KBM-802), 3-mercaptopropyltrimethoxysilane (KBM-803);
Sulfide groups and alkoxy-containing silane compounds such as bis (triethoxysilylpropyl) tetrasulfide (KBE-846);
Isocyanate groups and alkoxy-containing silane compounds such as 3-isocyanatopropyltriethoxysilane (KBE-9007) (all of which are manufactured by Shin-Etsu Silicone Co., Ltd .; trade names);
Is mentioned.

  Furthermore, vinyl group and acetoxy-containing silane compounds such as vinyltriacetoxysilane (Z-6075); allyl group and alkoxy-containing silane compounds exemplified by allyltrimethoxysilane (Z-6825); methyltrimethoxysilane (Z- 6366), dimethyldimethoxysilane (Z-6329), trimethylmethoxysilane (Z-6013), methyltriethoxysilane (Z-6383), methyltriphenoxysilane (Z-6721), ethyltrimethoxysilane (Z-6321) N-propyltrimethoxysilane (Z-6265), diisopropyldimethoxysilane (Z-6258), isobutyltrimethoxysilane (Z-2306), diisobutyldimethoxysilane (Z-6275), isobutyltriethoxysilane (Z-6403) , N-hexyltrimethoxysilane (Z-66583), n-hexyltriethoxysilane (Z-6586), cyclohexylmethyldimethoxysilane (Z-6187), n-octyl Alkyl group and alkoxy group-containing silane compounds such as triethoxysilane (Z-6341) and n-decyltrimethoxysilane (Z-6210); aryl groups and alkoxy groups such as phenyltrimethoxysilane (Z-6124) Silane compound; Alkyl group and chlorosilane group-containing silane compound such as n-octyldimethylchlorosilane (ACS-8); Silane compound that is an alkoxysilane such as tetraethoxysilane (Z-6697). Corning Co., Ltd .; trade name).

The reactive functional group-containing alkoxysiloxane is, among other things, an amino group and an alkoxy group-containing silane compound such as aminoalkyltrialkoxysiloxane or aminoalkylaminoalkyltrialkoxysiloxane. Since the amino group easily reacts with the surface-exposed reactive groups on the lower surface 10 _down of the first light-transmissive member 10 and the upper surface 20 _up of the second light-transmissive member 20, surface modification has a competitive priority. .

The amino group and alkoxy group-containing silane compound reacts with the surface-exposed reactive groups on the lower surface 10 _down of the first light transmissive member 10 and the upper surface 20 _up of the second light transmissive member 20 to modify the surface. Is not particularly limited, specifically, aminoalkylaminoalkyltrialkoxysiloxane, more specifically, H ₂ N- (C _p H _2p ) -NH- (C _q H _2q ) -Si ( -OC _r H _{2r + 1} ) ₃ (p, q, r are each independently a number of 1 to 6), preferably aminoethylaminopropyltrimethoxysilane (p = 2, q = 3, r = 1).

When one of the lower surface 10 _down of the first light transmissive member 10 and the surface on the joining side of the upper surface 20 _up of the second light transmissive member 20 is amplified with these plural vinyl group-containing alkoxysiloxanes, The other of the lower surface 10 _down of the first light transmissive member 10 and the upper surface 20 _up of the second light transmissive member 20 may be amplified with these plural vinyl group-containing alkoxysiloxanes, organic aluminate, inorganic Aluminate, organic titanate, inorganic titanate, triazine ring-containing compound, CH ₂ = CH-Si (-OCH ₃ ) ₃ (vinyl methoxysiloxane: VMS), CH ₂ = CH-Si (-OC ₂ H ₅ ) ₃ , CH _The reactivity may be enhanced by a silane coupling agent such as ₂ = CH-Si (-OC ₃ H ₇ ) ₃ .

As organic aluminate and / or organic titanate,
-{O-Si (-A ¹ ) (-B ¹ )}-
The repeating unit of-{O-Ti (-A ² ) (-B ² )}-is q units,
R units of repeating units of-{O-Al (-A ³ )}-(wherein p and q are 0 or a number of 2 to 200 and r is a number of 0 or 2 to 100) p + q + r> 2, and —A ¹ , —A ² and —A ³ are —CH ₃ , —C ₂ H ₅ , —CH═CH ₂ , —CH (CH ₃ ) _2, —CH ₂ CH (CH ₃ ) ₂ , —C (CH ₃ ) ₃ , —C ₆ H ₅ or —C ₆ H ₁₂ , —OCH ₃ , —OC ₂ H ₅ , —OCH═CH ₂ , —OCH (CH ₃ ) ₂ , —OCH ₂ CH (CH ₃ ) ₂ , —OC (CH ₃ ) ₃ , —OC ₆ H ₅ and —OC ₆ H ₁₂ and any one of the reactive groups that form the covalent bond, and —B ¹ and -B ² is a -N (CH ₃₎ COCH ₃ or _{-N (C 2 H 5) COCH} 3, -OCH 3, -OC 2 H 5, -OCH = CH 2, -OCH (CH 3) 2, -OCH ₂ CH (CH _{3) 2, -OC (CH 3} ) 3, -OC 6 H 5, -OC 6 H 12, -OCOCH 3, -OCOCH (C 2 H 5) C 4 H 9, -OCOC 6 H 5, -ON = C (CH _{3) 2} and -OC (CH ₃₎ = selected from CH ₂ be either a reactive group for forming the covalent bond, said repeating units p, the q, and r and positive In which at least ^one of -A ¹ , -A ² , -A ³ , -B ^1, and -B ² is the reactive group). In this compound, the repeating unit may be one obtained by block copolymerization or random copolymerization. An aluminate coupling agent such as organic aluminate or inorganic aluminate, or a titanate coupling agent such as organic titanate or inorganic titanate may be used.

（式(Ｉ)中、Ｗは、スペーサ基、例えば置換基を有していてもよいアルキレン基、アミノアルキレン基であってもよく、直接結合であってもよい。Ｙは、水酸基又は加水分解や脱離により水酸基を生成する反応性官能基、例えばトリアルコキシアルキル基である。−Ｚは、−Ｎ_３又は−ＮＲ^１Ｒ^２である（但し、Ｒ^１，Ｒ^２は同一又は異なりＨ又はアルキル基、−Ｒ^３Ｓｉ（Ｒ^４）_ｍ（ＯＲ^５）_３−ｍ[Ｒ^３，Ｒ^４はアルキル基、Ｒ^５はＨ又はアルキル基、ｍは０〜２]。なお、アルキレン基、アルコキシ、アルキル基は、置換基を有していてもよい炭素数１〜１２の直鎖状、分岐鎖状及び／又は環状の炭化水素基である。）で表わされるトリアジン化合物、例えば２，６−ジアジド−４−｛３−（トリエトキシシリル）プロピルアミノ｝−１，３，５−トリアジン（Ｐ−ＴＥＳ）；
アルコキシシリル基を有するチオール化合物、具体的にはトリアルコキシシリルアルキル基を有するチオール化合物；
アルコキシシリル基を有するエポキシ化合物、具体的にはトリアルキルオキシシリルアルキル基を有するエポキシ化合物；
アルコキシシリル基とメルカプト基とアジド基との少なくとも何れかを有するトリアジン化合物；
アルコキシシリル基を有するアミン化合物、具体的にはＮ−（３−（トリメトキシシリル）プロピル）エチレンジアミン；
が挙げられる。 More specifically, as the triazine ring-containing compound,
Amino group-containing compounds such as triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol (TES), aminoethylaminopropyltrimethoxysilane; trialkoxysilyl such as triethoxysilylpropylamino group Triazine compounds having an alkylamino group and a mercapto group or azide group, the following chemical formula (I)

(In Formula (I), W may be a spacer group, for example, an alkylene group which may have a substituent, an aminoalkylene group, or a direct bond. Y may be a hydroxyl group or a hydrolysis group. Or a reactive functional group that generates a hydroxyl group upon elimination, such as a trialkoxyalkyl group, -Z is -N ₃ or -NR ¹ R ² (provided that R ¹ and R ² are the same or different and H or alkyl _{^{group, -R 3 Si (R 4)}} m (oR 5) 3-m [R 3, R 4 is an alkyl group, ^{R 5} is H or an alkyl group, m is 0-2. in addition, an alkylene group, an alkoxy The alkyl group is a linear, branched and / or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.), For example, 2,6- Diazido-4- {3- (triethoxysilyl) propyl Amino} -1,3,5-triazine (P-TES);
A thiol compound having an alkoxysilyl group, specifically a thiol compound having a trialkoxysilylalkyl group;
An epoxy compound having an alkoxysilyl group, specifically, an epoxy compound having a trialkyloxysilylalkyl group;
A triazine compound having at least one of an alkoxysilyl group, a mercapto group, and an azide group;
An amine compound having an alkoxysilyl group, specifically N- (3- (trimethoxysilyl) propyl) ethylenediamine;
Is mentioned.

  As the silane coupling agent, a silane coupling agent such as a vinylalkoxysiloxane polymer; an amino group-containing silane coupling agent having an alkoxy group is preferable. Specific examples of such silane coupling agents include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602), N-2- (aminoethyl) -3-aminopropyltrimethoxy. Silane (KBM-603), N-2- (aminoethyl) -3-aminopropyltriethoxysilane (KBE-603), 3-aminopropyltrimethoxysilane (KBM-903), 3-aminopropyltriethoxysilane ( KBE-903), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573), N- ( An amino group-containing alkoxysilyl compound exemplified by the hydrochloride of vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane (KBM-575) (above, manufactured by Shin-Etsu Silicone Co., Ltd .; product name), 3-aminopropyltrimethoxysilane (Z-6610), 3-aminopropyl Trimethoxysilane (Z-6611), 3- (2-aminoethyl) aminopropyltrimethoxysilane (Z-6094), 3-phenylaminopropyltrimethoxysilane (Z-6883), N- [3- (trimethoxy Amino group-containing alkoxysilyl compounds exemplified by silyl) propyl] -N '-[(ethenylphenyl) methyl-1,2-ethanediamine hydrochloride (Z-6032) (above, manufactured by Toray Dow Corning Co., Ltd.) Product name) can be used preferably.

  Examples of amino group-free silane coupling agents having an alkoxy group include commercially available silane coupling agents, specifically vinyltrimethoxysilane (KBM-1003) and vinyltriethoxysilane (KBE-1003). 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303), 3-glycidoxypropylmethyldimethoxysilane (KBM-402), 3-glycol Epoxy group and alkoxy exemplified by Sidoxypropyltrimethoxysilane (KBM-403), 3-Glycidoxypropylmethyldiethoxysilane (KBE-402), 3-Glycidoxypropyltriethoxysilane (KBE-403) Group-containing silane coupling agent; styryl group and alkoxy group-containing silane coupling agent exemplified by p-styryltrimethoxysilane (KBM-1403); 3-methacryloxy Lopylmethyldimethoxysilane (KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropylmethyldiethoxysilane ( KBE-503), (meth) acryl group and alkoxy group-containing silane coupling agent exemplified by 3-acryloxypropyltrimethoxysilane (KBM-5103); exemplified by 3-ureidopropyltriethoxysilane (KBE-585) Ureido group and alkoxy-containing silane coupling agent; mercapto group and alkoxy-containing silane coupling agent exemplified by 3-mercaptopropylmethyldimethoxysilane (KBM-802) and 3-mercaptopropyltrimethoxysilane (KBM-803) A sulfide group exemplified by bis (triethoxysilylpropyl) tetrasulfide (KBE-846) and an alkoxy-containing silane Coupling agent; isocyanate group exemplified by 3-isocyanatopropyltriethoxysilane (KBE-9007) and alkoxy-containing silane coupling agent (all of which are manufactured by Shin-Etsu Silicone Co., Ltd .; trade name), and vinyl Vinyl group and acetoxy-containing silane coupling agent exemplified by triacetoxysilane (Z-6075); Allyl group and alkoxy-containing silane coupling agent exemplified by allyltrimethoxysilane (Z-6825); Methyltrimethoxysilane ( Z-6366), dimethyldimethoxysilane (Z-6329), trimethylmethoxysilane (Z-6013), methyltriethoxysilane (Z-6383), methyltriphenoxysilane (Z-6721), ethyltrimethoxysilane (Z- 6321), n-propyltrimethoxysilane (Z-6265), diisopropyldimethoxysilane (Z-6258), isobutyltrimethoxysilane (Z-2306), diisobutyldimethoxysilane (Z-6275), isobutyltriethoxysilane (Z-6403), n-hexyltrimethoxysilane (Z-6583), n-hexyltriethoxysilane (Z-6586), Alkyl group and alkoxy group-containing silane coupling agents exemplified by cyclohexylmethyldimethoxysilane (Z-6187), n-octyltriethoxysilane (Z-6341), n-decyltrimethoxysilane (Z-6210); Silane coupling agent containing aryl group and alkoxy group exemplified by methoxysilane (Z-6124); Silane coupling agent containing alkyl group and chlorosilane group exemplified by n-octyldimethylchlorosilane (ACS-8); Tetraethoxysilane A silane coupling agent which is an alkoxysilane exemplified by (Z-6697) (all of which are manufactured by Toray Dow Corning Co., Ltd .; trade name) is preferably used. Can.

In the optical member 1, the molecular adhesive bonded to the scattered hydroxyl groups scattered on the surface 10 _down of the first light transmissive member 10 is exposed to the exposed hydroxyl groups exposed on the surface 20 _up of the second light transmissive member 20. It is preferable that they are bonded to form a chemical bond.

In the optical member 1, at least one of the bonding side surface 10 _{down of} the first light transmissive member 10 and the bonding side surface 20 _{up of} the second light transmissive member 20 is subjected to a surface activation treatment. ,preferable.

  The optical member 1 is such that the surface activation treatment is at least one selected from, for example, corona discharge treatment, plasma treatment, and ultraviolet irradiation treatment.

A hydroxyl group having a sufficient concentration is formed on the bonding-side surfaces 10 _down and 20 _{up of the} light-transmitting members 10 and 20, or a reactive group concentration with the other hydroxyl group is amplified using a slightly generated hydroxyl group. There is a need to. In particular, one organic group-bonded hydroxyl group may be converted to an inorganic atom-bonded hydroxyl group, or a functional group that reacts with both organic group-bonded hydroxyl groups may be introduced.

Therefore, for example, when surface activation treatment such as corona discharge treatment, plasma treatment, or ultraviolet irradiation treatment is performed on at least one of the light-transmitting members 10 and 20 to be joined, the joint-side surface 10 _down · At 20 _up , the organic group generates a reactive group having high reactivity, for example, a hydroxyl group, and has a dotted hydroxyl group on the bonding surface where the original hydroxyl group and the newly formed hydroxyl group are exposed and scattered. It will be. If necessary, surface activation treatment is applied to both the light-transmitting members 10 and 20 to generate reactive groups, for example, hydroxyl groups, in which organic groups or inorganic molecules are highly reactive on the bonding-side surfaces 10 _down and 20 _up. As a result, the bonding surface 10 _down / 20 _up has hydroxyl groups exposed by interspersed with the original hydroxyl groups and newly formed hydroxyl groups. When a molecular adhesive is applied, sprayed, dipped, etc. on at least one of the light transmissive members 10 and 20, molecules of the molecular adhesive are bonded to hydroxyl groups scattered on the bonding side surface 10 _down and 20 _up , By superimposing the light-transmitting members 10 and 20 together, some of the hydroxyl groups scattered on the joint-side surfaces 10 _down and 20 _up generate a share via a molecular adhesive, thereby chemically bonding And it joins and the optical member 1 is obtained.

When the light-transmitting members 10 and 20 are bonded to each other, their bonded surfaces may be subjected to corona discharge treatment and overlapped at normal pressure, and then may be covalently bonded under normal pressure, but under reduced pressure or under pressure A covalent bond may be used. Access to an active group such as a hydroxyl group or a reactive functional group of a silane coupling agent that reacts with the active group is reduced or reduced under vacuum, for example, 50 torr or less, more specifically, reduced pressure of 50 to 10 torr, or 10 torr. Less than, more specifically less than 10 torr to 1 × 10 ⁻³ torr, preferably less than 10 torr to 1 × 10 ⁻² torr by removing the gaseous medium at the contact interface, or the contact It is accelerated by applying stress (load), eg 10-200 kgf, to the interface and further heating the contact interface.

As corona discharge treatment applied to the surfaces 10 _down and 20 _up of the light transmissive members 10 and 20, for example, using an atmospheric pressure corona surface reformer (manufactured by Shinko Electric Measurement Co., Ltd., product name: Corona Master), for example, , Power supply: AC 100 V, output voltage: 0 to 20 kV, oscillation frequency: 0 to 40 kHz, 0.1 to 60 seconds, temperature 0 to 60 ° C. Such a corona discharge treatment may be performed in a state of being wet with water, alcohols, acetones, esters, or the like.

The treatment applied to activate the surfaces 10 _down and 20 _up of the light transmissive members 10 and 20 is an atmospheric pressure plasma treatment and / or an ultraviolet irradiation treatment (a general UV treatment such as generating ozone by UV irradiation). Or excimer UV treatment).

  As the atmospheric pressure plasma treatment, for example, using an atmospheric pressure plasma generator (manufactured by Panasonic Corporation, product name: Aiplasma), for example, a plasma treatment speed of 10 to 100 mm / s, a power source: 200 or 220 V AC (30A), Compressed air: 0.5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, irradiation time: 0.1 to 60 seconds.

The ultraviolet irradiation process is performed using an excimer lamp light source (manufactured by Hamamatsu Photonics Co., Ltd., product name: L11751-01), for example, with an integrated light amount of 50 to 1500 mJ / cm ² .

  As shown in FIG. 2, the optical member 1 includes a first light transmissive member 10 that is a plano-convex lens 11 and a second light transmissive member 20 that is a flat plate joined via a molecular adhesive. It may be.

  As shown in FIG. 3A, the optical member 1 includes a plate-shaped first light-transmitting member 10 integrally molded with the convex side of the plano-convex lens 11 facing upward, and a muscle for flowing a liquid subject. The second optically transparent member 20, which is a base material sheet formed with a hollow spectroscopic analysis flow path 25, may be bonded via a molecular adhesive. When the subject flows through the spectroscopic analysis flow path 25, the light from the spectroscopic analysis light source is irradiated from the lower side of the optical member 1, and the second light transmissive member 20, the subject, and the first light transmissive member are irradiated. The light transmitted through 10 is refracted and converged by the plano-convex lens 11 and can be detected by a photodetector (not shown).

  As shown in FIG. 3B, the optical member 1 includes a plate-shaped first light-transmitting member 10 that is integrally molded with the concave side of the plano-concave lens 11 facing upward, and a muscle that flows a liquid subject. The second optically transparent member 20, which is a base material sheet formed with a hollow spectroscopic analysis flow path 25, may be bonded via a molecular adhesive. When the subject flows through the spectroscopic analysis flow path 25, the light from the spectroscopic analysis light source is irradiated from the lower side of the optical member 1, and the second light transmissive member 20, the subject, and the first light transmissive member are irradiated. The light transmitted through 10 is refracted and diffused by the plano-concave lens 11 and can be detected by a photodetector (not shown).

  As shown in FIG. 3C, the optical member 1 has a first light transmission integrally including an outer tube surrounding the plano-convex lens 11 with the convex side of the plano-convex lens 11 facing the first light-transmissive member 10. The member 10 and the plate-like second light transmissive member 20 may be joined via a molecular adhesive at the open end of the outer cylinder. Since no molecular adhesive is bonded to the plano-convex lens 11, the influence of the molecular adhesive can be avoided when light is transmitted to the plano-convex lens 11.

  The optical member 1 may be a microchemical chip as shown in FIG. An example of the microchemical chip is as shown in FIG. 4 showing the manufacturing process, and is overlapped with the first light-transmitting member 10 which is an addition-crosslinking type silicone flow path maintaining substrate sheet integrally formed with the lens 11 which also serves as a cover. A second optically transparent member 20, which is a base sheet formed by recessing a streak-like spectroscopic analysis flow path 25 through which a liquid specimen flows, is bonded via a molecular adhesive. It is a thing.

  The first light transmissive member 10 has a fluid sample injection hole 12a, 12b, a fluid sample discharge hole 13, and a fluid sample discharge hole 16a, 16b, 16c penetrating therethrough.

  To the second light-transmitting member 20 of the same size that overlaps the first light-transmitting member 10, the flow sample injection holes 12a and 12b, the flow sample discharge hole 13, and the flow analyte discharge holes 16a, 16b, and 16c. At corresponding positions, the flow sample injection sites 22a and 22b, the flow sample discharge site 23, and the flow analyte discharge sites 26a, 26b, and 26c are formed to be recessed. The flow path 24 branched from the flow sample injection holes 12a and 12b to join the flow sample discharge portion 23 and the downstream side toward the flow analyte discharge portions 26a, 26b, and 26c is recessed, and the second light transmission. It is formed on the sexual member 20. The spectroscopic analysis flow paths 25a, 25b, and 25c branching further downstream from the flow path 24 and extending to the flow analyte discharge sites 26a, 26b, and 26c are recessed and formed on the second light transmissive member 20. ing.

  Plano-concave lenses 11a, 11b, and 11c are formed on the upper surface of the first light transmitting member 10 at positions corresponding to the spectral analysis flow paths 25a, 25b, and 25c.

The lower surface 10 _down of the first light transmissive member 10 and the upper surface 20 _up of the second light transmissive member 20 are a flow sample injection site 22a, 22b, a flow sample discharge site 23, a flow path 24, and a flow for spectroscopic analysis. The surface is activated by corona treatment, plasma treatment, or ultraviolet irradiation treatment outside the area of the channels 25a, 25b, 25c and the flow specimen discharge sites 26a, 26b, 26c, and both members 10 and 20 are made of molecular adhesives. It is chemically bonded by a covalent bond through a monomolecular film.

The lower surface 20 _down of the second light transmissive member 20 is similarly bonded to the upper surface 30 _{up of} the third transmissive member 30 that also serves as a support by covalent bonding through a monomolecular film of a molecular adhesive. , May be chemically bonded.

  The optical member 1 which is this microchemical chip is used as follows. The sample stock solution is flowed from the flow sample injection hole 12a, the test liquid is flowed from the flow sample injection hole 12b, and joined and reacted while closing and releasing the flow path as necessary, and unnecessary liquid is allowed to flow through the flow sample discharge hole 13. Discharge. The subject is poured into the spectral analysis channels 25a, 25b, and 25c, and light from a spectral analysis light source such as infrared rays, ultraviolet rays, and laser light is irradiated from below the optical member 1 as necessary. The light is refracted, converged, and detected by a photodetector (not shown). Thereafter, the subject is discharged from the flow target discharge portions 26a, 26b, and 26c.

  In the optical member 1, the second light transmissive member may be a plate-shaped support, a sealing material enclosing the light emitting element, and a package molded body surrounding the light emitting element.

  A bonded sample of an optical member of an example to which the present invention is applied and an adhesive sample of an optical member of a comparative example to which the present invention is not applied were produced as follows, and their physical properties were evaluated.

(Examples 1-4)
Silicone: LSR-7070 (manufactured by Momentive Performance Materials Japan LLC, trade name) was used as an addition-crosslinking type silicone raw material composition that forms a transparent base material that is a first light transmissive member. After mixing the A and B agents of LSR-7070, pour them into a mold with a depth of 150 mm and a depth of 1.0 mm, heat them at 130 ° C. for 5 minutes, take them out of the molds, and further heat oven (manufactured by ASONE CORPORATION) ) Was annealed at 150 ° C. for 100 minutes to be cured into silicone, and the first light transmissive member was molded. The obtained first light transmissive member was rinsed with ethanol, washed, and air-dried. The surface of the first light transmitting member was subjected to surface treatment with a plasma surface treatment machine (manufactured by Sakai Semiconductor Co., Ltd.) at 20 kPa and 250 V for 30 seconds.

  On the other hand, polycarbonate (PC) plate-like transparent substrate: PC610 (manufactured by Takiron Co., Ltd., trade name), cycloolefin polymer (COP) plate-like transparent substrate: ZEONOR 1420R, ZEONOR Is a plate-like transparent substrate made of polymethyl methacrylate (PMMA), which is an acrylic resin: COMOGLASS DK3 (Kuraray Co., Ltd. is a registered trademark), a plate-like transparent substrate made of silicone (first light-transmissive member) The same quality). The second light transmissive member was rinsed with ethanol, washed, and air dried. On the surface of these second light transmissive members, an atmospheric pressure corona discharge treatment machine (manufactured by Shinko Electric Instrumentation Co., Ltd.), gap length: 1.0 mm, output voltage: 10 kV (surface voltage), moving speed: 4. Corona discharge treatment was performed under the conditions of 2 m / sec and number of movements: 3 times. Thereafter, a reactive functional group-containing alkoxysiloxane: SZ6020 (manufactured by Toray Dow Corning Co., Ltd.) and a plurality of vinyl group-containing alkoxysiloxane VMM-010 (manufactured by Amax Co., Ltd.), each of which is a mixed solution obtained by diluting 0.1 wt% in the same ethanol. It was applied and heated in a heating oven at 80 ° C. for 10 minutes to perform molecular adhesion treatment.

  The first light-transmitting member after treatment and each second light-transmitting member are bonded together, the remaining air on the bonding surface is pushed away with a plastic roller to release air, and then heated at 80 ° C. for 5 minutes. Crimping was performed to obtain a bonded sample of the optical member in which both members were bonded.

(Comparative Example 1)
A first light transmissive member LSR-7070 molded in the same manner as in the examples, and a plate-shaped transparent substrate made of cycloolefin polymer (COP) as a second light transmissive member: ZEONOR 1420R, ZEONOR is a registered trademark) An adhesive sample of an optical member obtained by bonding both members with a silicone adhesive SE9186L (manufactured by Toray Dow Corning Co., Ltd.) was obtained.

(Comparative Examples 2 to 4)
A first light transmissive member LSR-7070 molded in the same manner as in the examples, and a plate-shaped transparent substrate made of cycloolefin polymer (COP) as a second light transmissive member: ZEONOR 1420R, ZEONOR is a registered trademark) After that, the same surface treatment was performed, and then, a reactive functional group-containing alkoxysiloxane: SZ6020 (manufactured by Toray Dow Corning Co., Ltd.), a multi-vinyl group-containing alkoxysiloxane VMM-010 (manufactured by Amax Co., Ltd.), a single vinyl group-containing Alkoxysiloxane SZ6300 (manufactured by Toray Dow Corning Co., Ltd.) A solution obtained by diluting 0.1 wt% of each in another ethanol was applied and heated in a heating oven at 80 ° C. for 10 minutes to perform molecular adhesion treatment. Thereafter, pressure bonding was carried out in the same manner as in the Example to obtain a bonded sample of the optical member.

(Peel strength test)
About the joining sample of the optical member of Examples 1-4 and the adhesion sample of the optical member of Comparative Examples 1-4, the peeling strength was measured, respectively, and the state in the peeling surface was observed. The results are summarized in Tables 1 and 2.

  As is apparent from Table 1, all of the bonded samples of the optical members in which the first light transmissive member and the respective second light transmissive members are bonded by molecular adhesion are strong for covalent bonding by the molecular adhesive. It was joined to. Since silicone is a combination of elastic body and elastic body, the stress at the time of testing is different from other conditions, so it was only possible to calculate up to interface failure, but it was sufficient to bond because it was broken at the single layer of the rubber interface. I understand.

  As is apparent from Table 2, the silicone adhesive, the multi-vinyl group-containing alkoxysiloxane, and the single vinyl group-containing alkoxysiloxane did not adhere. Although the reactive functional group-containing alkoxysiloxane was bonded, the peel strength was lower than that of Example 1.

(Transmittance evaluation test)
The transmittance was measured for each of the bonded sample of the optical member of Example 1 and the bonded sample of the optical member of Comparative Example 1. In addition, as a control, a first transparent member formed in the example and a transparent transparent substrate made of cycloolefin polymer (COP), which is a second transparent member: ZEONOR 1420R (ZEONOR is a registered trademark) The transmittance of a sample obtained by pasting the first and second light-transmitting members together and pushing out the remaining air on the pasting surface with a plastic roller to remove air was measured. For the measurement, a spectrophotometer: UV-3150 (manufactured by Shimadzu Corporation, trade name) was used. FIG. 5 shows the transmittance of the optical member bonded sample and the optical member bonded sample using the first light transmissive member and the second light transmissive member in the same manner.

  As is clear from FIG. 5, all of the bonded samples of the optical member of Example 1 had substantially the same transmittance as that of the control bonded sample. In comparison, the adhesive sample of the optical member of Comparative Example 1 was found to have a decrease in transmittance due to the adhesive. In particular, a decrease in the transmittance at the low wavelength side, particularly 400 nm or less, was noticeable.

  The optical member of the present invention has an optical product that has high adhesive strength and must not be peeled off by light or heat, such as a lighting device, a light emitting device, a solar cell, a liquid crystal, an optical lens, a spectroscopic analyzer, a spectroscopic container, and many It is useful as a product in the field. Among these, it is useful for spectroscopic analysis such as a microchemical chip.

1 is an optical element, 10 is a first light transmitting member, 10 _down is a lower surface, 11, 11 a, 11 b, and 11 c are lenses, 12 a and 12 b are flow sample injection holes, 13 is a flow sample discharge hole, and 16 a, 16 b, 16c is a fluid analyte discharge hole, 20 is a second light transmissive member, 20 _up is an upper surface, 20 _down is a lower surface, 22a and 22b are fluid sample injection sites, 23 is a fluid sample ejection site, 24 is a flow path, 25a 25b and 25c are flow paths for spectroscopic analysis, 26a, 26b, and 26c are fluid analyte discharge sites, 30 is a third light transmitting member, and _30up is an upper surface.

Claims (14)

  A first light-transmitting member formed of addition-crosslinking type silicone and a second light-transmitting member formed of any one selected from polycarbonate, cycloolefin polymer, (meth) acrylic resin, silicone and glass The surface of at least one light-transmitting member is bonded to the surface-exposed reactive group, unsaturated group, epoxy group, ureido group, mercapto group, sulfide group, isocyanate group, plural alkoxysilyl groups, amino group, nitrile Having an amplification site amplified by a plurality of vinyl group-containing alkoxysiloxanes in a modified site surface-modified by a reactive functional group-containing alkoxysiloxane containing a functional group selected from a group and an azide group, An optical member, wherein the optical member is bonded to the surface of the other light-transmitting member via an amplification site.   The first light transmissive member and the second light transmissive member are bonded together by surface modification and amplification with the reactive functional group-containing alkoxysiloxane and the reactive functional group-containing alkoxysiloxane. The optical member according to claim 1.   The first light transmissive member and the second light transmissive member have the reactive functional group-containing alkoxysiloxane and the plural vinyl group-containing alkoxy on the surface exposed reactive group on the surface on the bonding side of each other. The optical member according to claim 1, wherein the optical member is bonded via a covalent bond of siloxane. The plural vinyl group-containing alkoxysiloxane has the following chemical formula:
R ² (OR ^1- ) ₂ -Si-O-[(CH ₂ = CH-) (OR ^1- ) Si-O] _n -Si (-OR ¹ ) ₂ R ³
(Wherein n is a number from ¹ to 20, R ¹ is C _a H _{2a + 1} , a is a number from 1 to 3, and R ² and R ³ are CH ₃ or CH ₂ = CH) The optical member according to claim 1, wherein the optical member is one.   The optical member according to claim 1, wherein the reactive functional group-containing alkoxysiloxane is a silane coupling agent.   The reactive functional group-containing alkoxysiloxane is an amino group and an alkoxy group-containing silane compound; a vinyl group and an alkoxy group-containing silane compound; an epoxy group and an alkoxy group-containing silane compound, a styryl group and an alkoxy group-containing silane compound; Group and alkoxy group-containing silane compound; ureido group and alkoxy-containing silane compound; mercapto group and alkoxy-containing silane compound; sulfide group and alkoxy-containing silane compound; isocyanate group and alkoxy-containing silane compound, allyl group and alkoxy-containing silane compound; And an alkoxy group-containing silane compound; an aryl group and an alkoxy group-containing silane compound; an alkyl group and a chlorosilane group-containing silane compound; and a tetraalkoxysilane compound. The optical member according to claim 1.   The optical member according to claim 6, wherein the reactive functional group-containing alkoxysiloxane is an aminoalkyltrialkoxysiloxane or the amino group and alkoxy group-containing silane compound that is an aminoalkylaminoalkyltrialkoxysiloxane. . The aminoalkylaminoalkyltrialkoxysiloxane has the following chemical formula:
H ₂ N- (C _p H _2p ) -NH- (C _q H _2q ) -Si (-OC _r H _{2r + 1} ) ₃
The optical member according to claim 7, wherein p, q, and r are each independently a number of 1 to 6.   At least one of the exposed surface of the first light transmissive member, the surface of the modified portion thereof, and the surface of the amplification portion thereof, and / or the exposed surface of the second light transmissive member and the modification thereof. The surface of the quality part and / or the surface of the amplification part thereof is a corona discharge treatment surface, a plasma treatment surface, an ultraviolet treatment surface, and / or an excimer treatment surface. Optical member.   The joint-side surface of the first light transmissive member and the second light transmissive member has, on the one hand, the modified portion and the amplification portion, and on the other hand, a silanepropyltriethoxysilane compound. It is a treated surface, a titanate compound treated surface, an aluminate compound treated surface, a thiol compound treated surface, an azide compound treated surface, a corona discharge treated surface, a plasma treated surface, an ultraviolet treated surface, and / or an excimer treated surface. The optical member according to claim 1.   The second light-transmitting member is a base on which a plate-like support, a sealing material enclosing the light emitting element, a package molded body surrounding the light emitting element, and a streak channel for flowing a liquid specimen are formed. The optical member according to claim 1, wherein the optical member is any one selected from a material sheet.   The optical member according to claim 1, wherein at least a part of the first light transmissive member is a lens.   The difference between the transmittance of the optical member and the transmittance when the first light transmissive member and the second light transmissive member are bonded to each other is 5% at the maximum. The optical member in any one of 1-5. A first light transmissive member formed of metal, polymer resin, crosslinked rubber, glass or ceramics, and a second light transmissive member formed of metal, polymer resin, crosslinked rubber, glass or ceramics A functional group selected from an unsaturated group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a plurality of alkoxysilyl groups, an amino group, a nitrile group, and an azide group is provided on the surface of at least one light transmitting member. Bonding of at least one light transmissive member between the first light transmissive member and the second light transmissive member by treating with the reactive functional group-containing alkoxysiloxane and the plural vinyl group-containing alkoxysiloxane. The surface exposed reactive group on the side surface is reacted with a reactive functional group-containing alkoxysiloxane to modify the surface to form a modified site. Forming an amplification region was amplified by the plurality vinyl-containing alkoxysiloxane quality site,
Bonding the surfaces on the bonding side of both the light transmissive members to obtain an optical member,
A method for manufacturing an optical member, comprising:

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