JP5724555B2 - Optical waveguide film and method for manufacturing optical waveguide film - Google Patents

Description

  The present invention relates to a photosensitive resin composition, an optical waveguide film, and a method for producing an optical waveguide film.

In recent years, in the optical communication field, flexible film-like optical waveguides (optical waveguide films) have been developed in place of quartz-based optical waveguides.
For example, Patent Document 1 discloses a technique for forming an optical waveguide by selectively irradiating a photocurable film with light and polymerizing a monomer.

International Publication No. 91/01505 Pamphlet JP 2008-158308 A

  In recent years, development of an optical waveguide film that suppresses the occurrence of light propagation loss has been desired.

  The present invention provides a photosensitive resin composition, an optical waveguide film, and a method for producing an optical waveguide film that can suppress the occurrence of light propagation loss.

According to the present invention,
(A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
A photosensitive resin composition is provided.

According to the present invention having this configuration, when light is applied to the photosensitive resin composition, an acid is generated from the photoacid generator, and the component (B) is polymerized only in the irradiated portion. Since the amount of the component (B) in the irradiated part is reduced, the component (B) in the non-irradiated part diffuses to the irradiated part in order to eliminate the concentration gradient generated between the irradiated part and the unirradiated part. A difference in refractive index occurs between the portion and the non-irradiated portion.
Moreover, if it heats after light irradiation, a component (B) will volatilize from an unirradiated part. As a result, a difference in refractive index occurs between the irradiated portion and the unirradiated portion. As a result, light can be reliably confined, and generation of light propagation loss can be suppressed.
In addition, in the present invention, the use of (A) and (B) can suppress the occurrence of light propagation loss.

  Here, the photosensitive resin composition is preferably for an optical waveguide.

Furthermore, the cyclic ether group in (B) is preferably an oxetanyl group or an epoxy group.
By making the cyclic ether group (B) an oxetanyl group or an epoxy group, the monomer can be stably polymerized.

The (A) is preferably a norbornene resin.
By using a norbornene-based resin as (A), it is possible to reliably increase the light transmittance at a specific wavelength, and to reliably reduce the propagation loss. Moreover, heat resistance can also be improved by using norbornene-type resin as (A).

Further, the refractive index of (B) is lower than that of (A), and the cyclic olefin resin of (A) is desorbed by an acid generated from the photoacid generator, and by desorption, It is preferable to have a leaving group that lowers the refractive index of the cyclic olefin resin.
By containing such a cyclic olefin resin, the refractive index of the region irradiated with light can be reliably lowered as compared with the unirradiated region.
In addition, since the refractive index of (B) is lower than that of (A), the monomer in the unirradiated part diffuses into the irradiated part, so that the refractive index of the region irradiated with light decreases. Thereby, the refractive index difference between the region irradiated with light and the non-irradiated region can be surely generated.

  The leaving group preferably has at least one of -O-, -Si-aryl structure, and -O-Si- structure. Among them, the leaving group is -Si- A diphenyl structure or an —O—Si-diphenyl structure is preferable.

Further, the cyclic olefin resin (A) preferably has a leaving group and an epoxy group in addition to the leaving group.
Thereby, since the cyclic olefin resin of (A) has an epoxy group, the crosslinking density of the optical waveguide film is increased by reacting with the component (B), thereby contributing to improvement of heat resistance. .

The photosensitive resin composition as described above can be used as a film for an optical waveguide.
Furthermore, an optical waveguide film manufactured by the following manufacturing method using the photosensitive resin composition as described above can be provided.
That is,
(A) a cyclic olefin resin;
(B) The refractive index is different from (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
In addition to selectively irradiating light to the photosensitive resin composition containing
An optical waveguide film can be provided in which the region irradiated with light is one of the cladding region and the core region, and the non-irradiated region is the other of the cladding region and the core region.

Moreover, according to the present invention,
(A) a cyclic olefin resin;
(B) The refractive index is different from (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
Having a layer made of a cured product obtained by curing
The layer has a core region and a pair of clad regions that are disposed across the core region and are adjacent to the core region,
The refractive index of the core region is higher than the refractive index of the cladding region,
An optical waveguide film in which the structure concentration derived from (B) in the core region and the structure concentration derived from (B) in the cladding region are different can be provided.

By making the structure concentration derived from (B) in the core region different from the structure concentration derived from (B) in the cladding region, a difference in refractive index between the core region and the cladding region can be reliably generated. And an optical waveguide film having a high light confinement effect.
Moreover, by using (A), the light transmittance in a specific wavelength can be improved and a propagation loss can be reduced.

Here, it is preferable that a difference in refractive index between the core region and the cladding region is 0.01 or more.
By doing so, the light can be reliably confined.
Furthermore, the (A) is preferably a norbornene resin.
By using a norbornene-based resin as (A), it is possible to reliably increase the light transmittance at a specific wavelength, and to reliably reduce the propagation loss.

The cyclic ether group (B) is preferably an oxetanyl group or an epoxy group.
By making the cyclic ether group in (B) an oxetanyl group or an epoxy group, monomers and oligomers can be stably polymerized.
Furthermore, it is preferable to have another pair of cladding regions arranged so as to sandwich the core region from a direction different from the pair of cladding regions.
Such an optical waveguide film is
(A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
A process of selectively irradiating light to a photosensitive resin composition comprising:
Heating the sensitive resin composition,
The light-irradiated region can be manufactured by one of the clad region and the core region, and the non-irradiated region can be manufactured by the other method of the clad region and the core region.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can suppress generation | occurrence | production of the propagation loss of light, an optical waveguide film, and the manufacturing method of an optical waveguide film are provided.

It is a figure which shows the manufacturing process of the optical waveguide film of this invention. It is a figure which shows the manufacturing process of the optical waveguide film of this invention. It is sectional drawing which shows the optical waveguide film of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
(Photosensitive resin composition)
First, the photosensitive resin composition will be described.
The photosensitive resin composition of the present embodiment is
(A) a cyclic olefin resin;
(B) The refractive index is different from (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
Is provided.
Such a photosensitive resin composition is used for a film including regions having different refractive indexes, for example, an optical waveguide film.
By using such a photosensitive resin composition, it is possible to provide an optical waveguide film or the like in which generation of light propagation loss is suppressed. In particular, when a curved optical waveguide is formed, generation of light propagation loss can be remarkably suppressed.

((A) Cyclic olefin resin)
The cyclic olefin resin (A) is added in order to ensure the film moldability of the photosensitive resin composition, and serves as a base polymer.
Here, the cyclic olefin resin may be unsubstituted, or hydrogen may be substituted with another group.
Examples of the cyclic olefin resin include norbornene resins and benzocyclobutene resins.
Especially, it is preferable to use norbornene-type resin from viewpoints, such as heat resistance and transparency.

As norbornene resin, for example,
(1) addition (co) polymer of norbornene type monomer obtained by addition (co) polymerization of norbornene type monomer,
(2) an addition copolymer of a norbornene monomer and ethylene or α-olefins,
(3) an addition polymer such as an addition copolymer of a norbornene-type monomer and a non-conjugated diene and, if necessary, another monomer;
(4) a ring-opening (co) polymer of a norbornene-type monomer, and a resin obtained by hydrogenating the (co) polymer if necessary,
(5) a ring-opening copolymer of a norbornene-type monomer and ethylene or α-olefins, and a resin obtained by hydrogenating the (co) polymer if necessary,
(6) Ring-opening copolymers such as norbornene-type monomers and non-conjugated dienes, or other monomers, and polymers obtained by hydrogenating the (co) polymers as necessary. Examples of these polymers include random copolymers, block copolymers, and alternating copolymers.

  These norbornene resins include, for example, ring-opening metathesis polymerization (ROMP), a combination of ROMP and a hydrogenation reaction, polymerization by radicals or cations, polymerization using a cationic palladium polymerization initiator, and other polymerization initiators ( For example, it can be obtained by any known polymerization method such as polymerization using a polymerization initiator of nickel or another transition metal).

  Among these, as the norbornene-based resin, an addition (co) polymer is preferable. Addition (co) polymers are also preferred because they are rich in transparency, heat resistance and flexibility. For example, after forming a film with the photosensitive resin composition, an electrical component or the like may be mounted via solder. In such a case, an addition (co) polymer is preferable because it needs to have high heat resistance, that is, reflow resistance. Further, when a film is formed from the photosensitive resin composition and incorporated in a product, it may be used in an environment of about 80 ° C., for example. Even in such a case, an addition (co) polymer is preferred because it is necessary to have heat resistance.

  Among them, the norbornene-based resin preferably includes a norbornene repeating unit having a substituent containing a polymerizable group or a norbornene repeating unit having a substituent containing an aryl group.

  As the repeating unit of norbornene having a substituent containing a polymerizable group, the repeating unit of norbornene having a substituent containing an epoxy group, the repeating unit of norbornene having a substituent containing a (meth) acryl group, and an alkoxysilyl group At least one of the repeating units of norbornene having a substituent containing is preferable. These polymerizable groups are preferable because of their high reactivity among various polymerizable groups.

  Moreover, if the thing containing 2 or more types of norbornene repeating units containing such a polymeric group is used, both flexibility and heat resistance can be achieved.

  On the other hand, by including a norbornene repeating unit having a substituent containing an aryl group, the aryl group has extremely high hydrophobicity, and therefore, dimensional change due to water absorption can be prevented more reliably.

  Furthermore, the norbornene-based polymer preferably contains an alkylnorbornene repeating unit. The alkyl group may be linear or branched.

  By including the repeating unit of alkyl norbornene, the norbornene-based polymer has high flexibility, and thus can provide high flexibility (flexibility).

  A norbornene-based polymer containing an alkylnorbornene repeating unit is also preferable because of its excellent transmittance with respect to light in a specific wavelength region (particularly, a wavelength region near 850 nm).

  Therefore, as the norbornene-based resin, those represented by the following formulas (1) to (4) and (8) to (10) are preferable.

(In Formula (1), R ₁ represents an alkyl group having 1 to 10 carbon atoms, a represents an integer of 0 to 3, b represents an integer of 1 to 3, and p ₁ / q ₁ is 20 or less.)
The norbornene-based resin of the formula (1) can be produced as follows.
(1) is obtained by dissolving norbornene having R ₁ and norbornene having an epoxy group in the side chain in toluene, and solution polymerization using Ni compound (A) as a catalyst.

In addition, the manufacturing method of norbornene which has an epoxy group in a side chain is as (i) (ii), for example.
(I) Synthesis of norbornene methanol (NB—CH ₂ —OH) CPD (cyclopentadiene) and α olefin (CH ₂ ═CH—CH ₂ —OH) produced by cracking DCPD (dicyclopentadiene) at high temperature and high pressure React.

(Ii) Synthesis of epoxy norbornene It is formed by the reaction of norbornene methanol and epichlorohydrin.

In the formula (1), when b is 2 or 3, an epichlorohydrin in which the methylene group is an ethylene group, a propylene group or the like is used.
Among the norbornene-based resins represented by the formula (1), from the viewpoint that both flexibility and heat resistance can be achieved, in particular, R ₁ is an alkyl group having 4 to 10 carbon atoms, and a and A compound in which each b is 1, for example, a copolymer of butylbornene and methyl glycidyl ether norbornene, a copolymer of hexyl norbornene and methyl glycidyl ether norbornene, a copolymer of decyl norbornene and methyl glycidyl ether norbornene, or the like is preferable.

(In Formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, R ₃ represents a hydrogen atom or a methyl group, c represents an integer of 0 to 3, and p ₂ / q _2. Is 20 or less.)
The norbornene-based resin of the formula (2) is obtained by dissolving norbornene having R ₂ and norbornene having acryl and methacrylic groups in the side chain in toluene and performing solution polymerization using the above-described Ni compound (A) as a catalyst. Can be obtained.

Among the norbornene-based polymers represented by the formula (2), R ₂ is an alkyl group having 4 to 10 carbon atoms and c is 1 from the viewpoint of achieving both flexibility and heat resistance. Compounds such as copolymers of butylbornene and 2- (5-norbornenyl) methyl acrylate, copolymers of hexylnorbornene and 2- (5-norbornenyl) methyl acrylate, decylnorbornene and 2- (5-norbornenyl) methyl acrylate And a copolymer thereof are preferred.

(In Formula (3), R ₄ represents an alkyl group having 1 to 10 carbon atoms, each X ₃ independently represents an alkyl group having 1 to 3 carbon atoms, and d represents 0 to 3 carbon atoms. Represents an integer, and p ₃ / q ₃ is 20 or less.)
The resin of the formula (3) can be obtained by dissolving norbornene having R ₄ and norbornene having an alkoxysilyl group in the side chain in toluene, and solution polymerization using the above-described Ni compound (A) as a catalyst. it can.

Among the norbornene-based polymers represented by the formula (3), in particular, a compound in which R ₄ is an alkyl group having 4 to 10 carbon atoms, d is 1 or 2, and X ₃ is a methyl group or an ethyl group, For example, a copolymer of butylbornene and norbornenylethyltrimethoxysilane, a copolymer of hexylnorbornene and norbornenylethyltrimethoxysilane, a copolymer of decylnorbornene and norbornenylethyltrimethoxysilane, butylbornene and triethoxysilylnorbornene Copolymer of hexyl norbornene and triethoxysilyl norbornene, copolymer of decyl norbornene and triethoxysilyl norbornene, copolymer of butylbornene and trimethoxysilyl norbornene, hexyl norbornene And copolymers of trimethoxysilyl norbornene, copolymers, etc. of decyl norbornene and trimethoxysilyl norbornene are preferred.

(In the formula, R ₅ represents an alkyl group having 1 to 10 carbon atoms, and A ₁ and A ₂ each independently represent a substituent represented by the following formulas (5) to (7), (It is not the same substituent at the same time, and p ₄ / q ₄ + r is 20 or less.)
(4) is obtained by dissolving norbornene having R ₅ and norbornene having A ₁ and A ₂ in the side chain in toluene and solution polymerization using Ni compound (A) as a catalyst.

(In formula (5), e represents an integer of 0 to 3, and f represents an integer of 1 to 3.)

(In formula (6), R ₆ represents a hydrogen atom or a methyl group, and g represents an integer of 0 to 3.)

(Equation (7) in, _{X 4} each independently represents an alkyl group having 1 to 3 carbon atoms, h is. Represents an integer of 0 to 3)

  In addition, as a norbornene-type polymer represented by Formula (4), for example, any of butyl norbornene, hexyl norbornene or decyl norbornene, 2- (5-norbornenyl) methyl acrylate, norbornenyl ethyltrimethoxysilane, Terpolymer with either triethoxysilyl norbornene or trimethoxysilyl norbornene, terpolymer of butylbornene, hexylnorbornene or decylnorbornene, 2- (5-norbornenyl) methyl acrylate and methylglycidyl ether norbornene, butylbornene, Either hexyl norbornene or decyl norbornene and methyl glycidyl ether norbornene, norbornenyl ethyltrimethoxysilane, triethoxysilyl Terpolymers, etc. with either Ruborunen or trimethoxysilyl norbornene.

(In formula (8), R ₇ represents an alkyl group having 1 to 10 carbon atoms, R ₈ represents a hydrogen atom, a methyl group or an ethyl group, Ar represents an aryl group, and X ₁ represents oxygen. X ₂ represents a carbon atom or a silicon atom, i represents an integer of 0 to 3, j represents an integer of 1 to 3, and p ₅ / q ₅ is 20 or less. is there.)
Norbornene containing R ₇ and norbornene containing — (CH ₂ ) —X ₁ —X ₂ (R ₈ ) _{3 -j} (Ar) _j in the side chain are dissolved in toluene, and solution polymerization is performed using a Ni compound as a catalyst. (8) is obtained.

Of the norbornene polymers represented by the formula (8), those in which X ₁ is an oxygen atom, X ₂ is a silicon atom, and Ar is a phenyl group are preferable.
Further, particularly from the viewpoint of flexibility, heat resistance and refractive index control, R ₇ is an alkyl group having 4 to 10 carbon atoms, X ₁ is an oxygen atom, X ₂ is a silicon atom, Ar is a phenyl group, R _A compound in which ₈ is a methyl group, i is 1 and j is 2, for example, a copolymer of butylbornene and diphenylmethylnorbornenemethoxysilane, a copolymer of hexylnorbornene and diphenylmethylnorbornenemethoxysilane, decylnorbornene and diphenylmethylnorbornenemethoxysilane Of these, the copolymer is preferred.

  Specifically, it is preferable to use the following norbornene resin.

(R ₇ , R ₈ , p ₅ , q ₅ , and i in Formula (9) are the same as in Formula (8).)

From the viewpoint of flexibility, heat resistance, and refractive index control, in Formula (8), R ₇ is an alkyl group having 4 to 10 carbon atoms, X ₁ is a methylene group, X ₂ is a carbon atom, and Ar is Compounds having a phenyl group, R ₈ is a hydrogen atom, i is 0, and j is 1, for example, a copolymer of butylbornene and phenylethylnorbornene, a copolymer of hexylnorbornene and phenylethylnorbornene, a copolymer of decylnorbornene and phenylethylnorbornene Etc.
Further, the following may be used as the norbornene resin.

（式（１０）において、Ｒ_１０は、炭素数１〜１０のアルキル基を表し、Ｒ_１１は、アリール基を示し、ｋは０以上、４以下である。ｐ_６／ｑ_６は２０以下である。）

(In Formula (10), R ₁₀ represents an alkyl group having 1 to 10 carbon atoms, R ₁₁ represents an aryl group, and k is 0 or more and 4 or less. P ₆ / q ₆ is 20 or less. is there.)

P ₁ / q _{1 to} p ₃ / q ₃ , p ₅ / q ₅ , p ₆ / q ₆ or p ₄ / q ₄ + r may be 20 or less, preferably 15 or less, About 0.1-10 is more preferable. Thereby, the effect including the repeating unit of multiple types of norbornene is exhibited.

The norbornene-based resin as described above preferably has a leaving group. Here, the leaving group is a group that is released by the action of an acid.
Specifically, those having at least one of an —O— structure, an —Si—aryl structure, and an —O—Si— structure in the molecular structure are preferable. Such an acid leaving group is released relatively easily by the action of a cation.

Among these, as the leaving group that causes a decrease in the refractive index of the resin by leaving, at least one of the -Si-diphenyl structure and the -O-Si-diphenyl structure is preferable.
For example, among the norbornene polymers represented by the formula (8), those in which X ₁ is an oxygen atom, X ₂ is a silicon atom, and Ar is a phenyl group have a leaving group.
In the formula (3), there is a case where the Si—O—X ₃ part of the alkoxysilyl group is eliminated.

  For example, when the norbornene resin of formula (9) is used, it is presumed that the reaction proceeds as follows by the acid generated from the photoacid generator (denoted as PAG). Here, only the leaving group portion is shown, and the case where i = 1 is described.

Furthermore, in addition to the structure of the formula (9), the side chain may have an epoxy group. By using such a material, there is an effect that a film having excellent adhesion can be formed.
A specific example is as follows.

(In formula (31), p ₇ / q ₇ + r ₂ is 20 or less.)
The compound represented by the formula (31) includes, for example, hexyl norbornene, diphenylmethyl norbornene methoxysilane (norbornene containing -CH ₂ -O-Si (CH ₃ ) (Ph) ₂ in the side chain) and epoxy norbornene in toluene. It can be obtained by dissolving and solution polymerization using a Ni compound as a catalyst.

((B) Monomer having a cyclic ether group, oligomer having a cyclic ether group)
Next, the component (B) will be described.
(B) is at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group. The component (B) may be any component that has a refractive index different from that of the resin (A) and is compatible with the resin (A). The refractive index difference between the component (B) and the resin (A) is preferably 0.01 or more.
The refractive index of the component (B) may be higher than that of the resin (A), but the component (B) preferably has a lower refractive index than that of the resin (A).

The monomer having a cyclic ether group (B) and the oligomer having a cyclic ether group are polymerized by ring-opening in the presence of an acid. Considering the diffusibility of the monomer and oligomer, the molecular weight (weight average molecular weight) of the monomer and the molecular weight (weight average molecular weight) of the oligomer are preferably 100 or more and 400 or less, respectively.
(B) has, for example, an oxetanyl group or an epoxy group. Such a cyclic ether group is preferable because it is easily opened by an acid.

  As the monomer having an oxetanyl group and the oligomer having an oxetanyl group, those selected from the following formulas (11) to (20) are preferable. By using these, there is an advantage that transparency is excellent in the vicinity of a wavelength of 850 nm and that both flexibility and heat resistance are possible. These may be used alone or in combination.

  In Formula (18), n is 0 or more and 3 or less.

  Especially, it is preferable to use Formula (13), (15), (16), (17), (20) from a viewpoint of ensuring the refractive index difference with resin of (A).

Further, considering the point that there is a difference in refractive index from the resin of (A), the point that the molecular weight is small, the mobility of the monomer is high, and the point that the monomer does not easily volatilize, the equations (20) and (15) It is particularly preferred to use it.
Moreover, as a compound which has an oxetanyl group, the following formula | equation (32) and Formula (33) can be used. Formula (32) can use Toagosei's trade name TESOX, etc., and Formula (33) can use Toagosei's trade name OX-SQ.

(In formula (33), n is 1 or 2)

Examples of the monomer having an epoxy group and the oligomer having an epoxy group include the following. The monomer and oligomer having an epoxy group are polymerized by ring-opening in the presence of an acid.
As the monomer having an epoxy group and the oligomer having an epoxy group, those represented by the following formulas (34) to (39) can be used. Especially, it is preferable to use an alicyclic epoxy monomer (36)-(39) from a viewpoint that the distortion energy of an epoxy ring is large and is excellent in reactivity.
In addition, Formula (34) is an epoxy norbornene, for example, ProNB's EpNB can be used. Formula (35) is γ-glycidoxypropyltrimethoxysilane. For example, Z-6040 manufactured by Toray Dow Corning Silicone Co., Ltd. can be used. Formula (36) is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. For example, E0327 manufactured by Tokyo Chemical Industry can be used.
Further, the formula (37) is 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexenecarboxylate, and for example, Celoxide 2021P manufactured by Daicel Chemical Industries, Ltd. can be used. Formula (38) is 1,2-epoxy-4-vinylcyclohexane, and Celoxide 2000 manufactured by Daicel Chemical Industries, Ltd. can be used.
Further, the formula (39) is 1,2: 8,9 diepoxy limonene, and for example, (Celoxide 3000 manufactured by Daicel Chemical Industries) can be used.

Furthermore, as the component (B), a monomer having an oxetanyl group, an oligomer having an oxetanyl group, a monomer having an epoxy group, and an oligomer having an epoxy group may be used in combination.
Monomers having an oxetanyl group and oligomers having an oxetanyl group have a slow initiation reaction but a fast growth reaction. On the other hand, a monomer having an epoxy group and an oligomer having an epoxy group have a fast initiation reaction for initiating polymerization, but have a slow growth reaction. Therefore, by using a monomer having an oxetanyl group, an oligomer having an oxetanyl group, a monomer having an epoxy group, and an oligomer having an epoxy group, when irradiated with light, the light irradiated portion and the unirradiated portion A difference in refractive index can be reliably generated.
The component (B) is preferably 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the component (A). Of these, 2 parts by weight or more and 20 parts by weight or less are preferable. Thereby, the refractive index modulation between the core and the clad is possible, and there is an effect that both flexibility and heat resistance can be achieved.

((C) Photoacid generator)
Any photoacid generator may be used as long as it absorbs light energy to generate Bronsted acid or Lewis acid. For example, triphenylsulfonium trifluoromethanesulfonate, tris (4-t-butylphenyl) sulfonium- Sulfonium salts such as trifluoromethanesulfonate, diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate, ammonium salts, phosphonium salts, diphenyliodonium trifluoromethanesulfonate, iodonium salts such as (triccumyl) iodonium-tetrakis (pentafluorophenyl) borate, Quinonediazides, diazomethanes such as bis (phenylsulfonyl) diazomethane, 1-phenyl-1- (4-methylphenyl) sulfonyl Sulfonic esters such as oxy-1-benzoylmethane and N-hydroxynaphthalimide-trifluoromethanesulfonate, disulfones such as diphenyldisulfone, tris (2,4,6-trichloromethyl) -s-triazine, 2- ( And compounds such as triazines such as 3.4-methylenedioxyphenyl) -4,6-bis- (trichloromethyl) -s-triazine. These photoacid generators can be used alone or in combination.

  The content of the photoacid generator is preferably 0.01 parts by weight or more and 0.3 parts by weight or less with respect to 100 parts by weight of the component (A). Especially, 0.02 weight part or more and 0.2 weight part or less are preferable. Thereby, there exists an effect of a reactive improvement.

The photosensitive resin composition may contain additives such as a sensitizer in addition to the above components (A), (B), and (C).
The sensitizer increases the sensitivity of the photoacid generator to light and is suitable for reducing the time and energy required for activation (reaction or decomposition) of the photoacid generator and for activating the photoacid generator. It has a function of changing the wavelength of actinic radiation to the wavelength.
Such a sensitizer is appropriately selected according to the sensitivity of the photoacid generator and the peak wavelength of absorption of the sensitizer, and is not particularly limited. For example, 9,10-dibutoxyanthracene (CAS No. 76275) is selected. -14-4) anthracenes, xanthones, anthraquinones, phenanthrenes, chrysene, benzpyrenes, fluoranthenes, rubrenes, pyrenes, indanthrines, thioxanthen-9-one (Thioxanthen-9-ones) are used alone or as a mixture.

Specific examples of the sensitizer include 2-isopropyl-9H-thioxanthen-9-one, 4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone, phenothiazine, and these Of the mixture.
The content of the sensitizer in the photosensitive resin composition is preferably 0.01% by weight or more, more preferably 0.5% by weight or more, and further preferably 1% by weight or more. preferable. In addition, it is preferable that an upper limit is 5 weight% or less.

Next, the manufacturing method of the optical waveguide film which uses the above photosensitive resin compositions is demonstrated.
Here, a method for producing an optical waveguide film using a photosensitive resin composition in which the component (B) has a refractive index lower than that of the cyclic olefin resin (A) will be described.

First, as shown in FIG. 1 (A), a photosensitive resin composition is dissolved in a solvent to form a varnish 1, and this varnish 1 is applied onto a substrate 2.
Examples of the solvent for adjusting the photosensitive resin composition to varnish include, for example, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), Ether solvents such as anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cellosolv solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane , Toluene, xylene, benzene, mesitylene and other aromatic hydrocarbon solvents, pyridine, pyrazine, furan, pyrrole, thiophene, methylpyrrolidone and other aromatic heterocyclic compounds Amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), halogen compound solvents such as dichloromethane, chloroform and 1,2-dichloroethane, ethyl acetate, methyl acetate, ethyl formate, etc. Ester solvents, various organic solvents such as sulfur compound solvents such as dimethyl sulfoxide (DMSO) and sulfolane, or mixed solvents containing them.

Next, after apply | coating the varnish 1 on the base material 2, it is made to dry and a solvent is evaporated (desolvent). Thereby, as shown to FIG. 1 (B), the varnish 1 becomes the film 11 for optical waveguide formation.
Here, examples of the method for applying the varnish 1 include a doctor blade method, a spin coating method, a dipping method, a table coating method, a spray method, an applicator method, a curtain coating method, and a die coating method. It is not limited. For the base material 2, for example, a sheet having a refractive index lower than that of a core region 112 described later is used. For example, a sheet containing a norbornene-based resin and an epoxy resin is used.

Next, the film 11 is selectively irradiated with light (for example, ultraviolet rays).
As shown in FIG. 2A, a mask M having an opening formed above the film 11 is disposed. The film 11 is irradiated with light through the opening of the mask M.
In the film 11 in the region irradiated with light, an acid is generated from the photoacid generator. The component (B) is polymerized by the generated acid.
In the region not irradiated with light, no acid is generated from the photoacid generator, so that component (B) is not polymerized. In the irradiated part, since the component (B) is polymerized to become a polymer, the amount of the component (B) decreases. Thereby, the component (B) of an unirradiated part diffuses to an irradiated part, and thereby a refractive index difference occurs between the irradiated part and the unirradiated part.
Here, when the component (B) has a lower refractive index than the cyclic olefin resin, the component (B) of the unirradiated part diffuses into the irradiated part, and the refractive index of the unirradiated part increases. The refractive index of the irradiated part is lowered.
In addition, the refractive index difference between the polymer obtained by polymerizing the component (B) and the monomer having a cyclic ether group is about 0 or more and 0.001 or less, and the refractive indexes are considered to be substantially the same.

Further, when a cyclic olefin resin having a leaving group is used as (A), the following action occurs.
In the portion irradiated with light, the leaving group of the cyclic olefin resin is eliminated by the acid generated from the photoacid generator. In the case of a leaving group such as a -Si-aryl structure, a -Si-diphenyl structure, and a -O-Si-diphenyl structure, the refractive index of the resin decreases due to the leaving. For this reason, the refractive index of the irradiated portion is lowered.

  Thus, when the photosensitive resin composition of this embodiment is used, it is possible to start a polymerization of a component (B) with the acid generate | occur | produced from a photo-acid generator.

Next, the film 11 is heated. In this heating step, the component (B) of the irradiated portion irradiated with light is further polymerized. On the other hand, in this heating step, the component (B) in the unirradiated part is volatilized. Thereby, in an unirradiated part, a component (B) decreases and it becomes a refractive index close | similar to cyclic olefin resin.
In this film 11, as shown in FIG. 2B, the region irradiated with light becomes the cladding region 111, and the non-irradiated region becomes the core region 112. The refractive index of the core region 112 is higher than the refractive index of the cladding region 111, and the structure concentration derived from the (B) in the core region 112 is different from the structure concentration derived from the (B) in the cladding region 111. . Specifically, the structure concentration derived from (B) in the core region 112 is low in the structure concentration derived from (B) in the cladding region.
The clad region 111 has a refractive index lower than that of the core region 112, and the refractive index difference between the clad region 111 and the core region 112 is 0.01 or more.
Thereafter, a film similar to the base material 2 is stuck on the film 11. The pair of base materials 2 become clad regions arranged so as to sandwich the core region 112 from a direction different from the clad region 111.
Through the above steps, the optical waveguide film 3 is obtained as shown in FIG.

Next, the effect of this embodiment is demonstrated.
When light is applied to the photosensitive resin composition of the present embodiment, an acid is generated from the photoacid generator, and the component (B) is polymerized only in the irradiated portion. Since the amount of the component (B) in the irradiated part decreases, the component (B) in the non-irradiated part diffuses into the irradiated part, thereby causing a refractive index difference between the irradiated part and the unirradiated part. Specifically, in this embodiment, since a substituted or unsubstituted cyclic olefin resin having a higher refractive index than that of the component (B) is used as the base polymer, the component (B) in the unirradiated portion is irradiated with the irradiated portion. The refractive index of the unirradiated part becomes higher than the refractive index of the irradiated part.
In addition to this, when the photosensitive resin composition is heated after light irradiation, the component (B) volatilizes from the unirradiated portion. Thereby, a refractive index difference further occurs between the irradiated portion and the unirradiated portion.
Thus, by using the photosensitive resin composition, a refractive index difference can be reliably formed between the irradiated portion and the unirradiated portion.

Patent Document 2 discloses a technique for crosslinking a norbornene-based resin having an oxetanyl group or the like with a thermal acid generator. However, the composition disclosed in Patent Document 2 contains a norbornene resin having an oxetanyl group or the like as a base polymer. And the whole composition is heated and a crosslinked structure is produced in the whole composition. Therefore, in Patent Document 2, by selectively irradiating light and generating an acid, polymerization is selectively caused, and the monomer diffuses in a region where the monomer concentration is reduced, resulting in a concentration difference. There is no technical idea at all.
In contrast, when the photosensitive resin composition of the present embodiment is selectively irradiated with light, the amount of the component (B) in the irradiated portion is reduced due to the generation of acid, so the component (B) in the unirradiated portion is reduced. It has been found that a difference in refractive index occurs between the irradiated portion and the unirradiated portion due to diffusion to the irradiated portion.

In addition, when the cyclic olefin resin has a leaving group that is desorbed by an acid generated from the photoacid generator and reduces the refractive index of the cyclic olefin resin of (A) by desorption, The refractive index of the region irradiated with can be reliably reduced as compared with the unirradiated region.
On the other hand, when the cyclic olefin resin has no leaving group, the side chain is chemically stable, so the refractive index of the core region and the cladding region depends on conditions such as light irradiation and heating. Can be prevented from fluctuating.

Furthermore, in this embodiment, norbornene-type resin is used as (A). Thereby, the light transmittance in a specific wavelength can be improved reliably, and reduction of propagation loss can be aimed at reliably.
In addition, the clad region 111 has a lower refractive index than the core region 112, and by making the difference in refractive index between the clad region 111 and the core region 112 0.01 or more, light confinement can be reliably performed. The occurrence of light propagation loss can be suppressed.

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in the said embodiment, although the optical waveguide film was formed using the photosensitive resin composition, you may use for a hologram etc., for example not only in this. The photosensitive resin composition of the present invention is suitable for forming a film in which a region having a high refractive index and a region having a low refractive index are mixed.

Next, examples of the present invention will be described.
Example 1
(1) Synthesis of norbornene-based resin having a leaving group In a glove box filled with dry nitrogen in which the water and oxygen concentrations are both controlled to 1 ppm or less, 7.2 g (40.1 mmol) of hexylnorbornene (HxNB) ), 12.9 g (40.1 mmol) of diphenylmethylnorbornene methoxysilane was weighed into a 500 mL vial, 60 g of dehydrated toluene and 11 g of ethyl acetate were added, and the top was sealed with a silicon sealer.
Next, 1.56 g (3.2 mmol) of Ni catalyst represented by the following chemical formula (B) and 10 mL of dehydrated toluene are weighed in a 100 mL vial, put a stirrer chip and sealed, and the catalyst is thoroughly stirred to completely Dissolved in.
When 1 mL of the Ni catalyst solution represented by the following chemical formula (B) is accurately weighed with a syringe, and quantitatively injected into the vial bottle in which the above two types of norbornene are dissolved, and stirred at room temperature for 1 hour, a marked increase in viscosity occurs. Was confirmed. At this point, the stopper was removed, 60 g of tetrahydrofuran (THF) was added, and the mixture was stirred to obtain a reaction solution.
In a 100 mL beaker, 9.5 g of acetic anhydride, 18 g of hydrogen peroxide (concentration 30%) and 30 g of ion-exchanged water were added and stirred to prepare an aqueous solution of peracetic acid on the spot. Next, the total amount of this aqueous solution was added to the above reaction solution and stirred for 12 hours to reduce Ni.
Next, the treated reaction solution was transferred to a separatory funnel, the lower aqueous layer was removed, and then 100 mL of a 30% aqueous solution of isopropyl alcohol was added and vigorously stirred. The aqueous layer was removed after standing and completely separating the two layers. After repeating this water washing process three times in total, the oil layer was dropped into a large excess of acetone to reprecipitate the polymer produced, separated from the filtrate by filtration, and then in a vacuum dryer set at 60 ° C. Polymer # 1 was obtained by heating and drying for 12 hours. The molecular weight distribution of polymer # 1 is Mw = 100,000 according to GPC measurement, Mn = 40,000, and the molar ratio of each structural unit in polymer # 1 is 50 mol% hexylbornene structural unit according to NMR identification. The methylnorbornene methoxysilane structural unit was 50 mol%. The refractive index was 1.55 (measurement wavelength: 633 nm) by Metricon.

(Method for producing photosensitive resin composition)
10 g of the purified polymer # 1 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of antioxidant Irganox 1076 (manufactured by Ciba Geigy), cyclohexyloxetane monomer (shown by Formula 20, CHOX manufactured by Toa Gosei Co., Ltd.) CAS # 483303-3-25-9, molecular weight 186, boiling point 125 ° C./1.33 kPa) 2 g, photoacid generator Rhodosil Photoinitiator 2074 (manufactured by Rhodia, CAS # 178233-72-2) (1.36E-2 g, ethyl acetate 0. In 1 mL) and uniformly dissolved, followed by filtration through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V1.

(Method for producing optical waveguide film)
(Preparation of lower cladding)
A photosensitive norbornene resin composition (Avatrel 2000P varnish manufactured by Promeras Co., Ltd.) was uniformly applied on a silicon wafer with a doctor blade, and then placed in a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, the entire coated surface was irradiated with 100 mJ of ultraviolet light and heated in a dryer at 120 ° C. for 1 hour to cure the coating film to form a lower clad. The formed lower clad had a thickness of 20 μm, was colorless and transparent, and had a refractive index of 1.52 (measurement wavelength: 633 nm).
(Formation of core region and cladding region)
After the photosensitive resin composition varnish V1 was uniformly applied on the lower clad by a doctor blade, it was put into a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
A dry film in which Avatrel 2000P is laminated in advance on a polyethersulfone (PES) film so as to have a dry thickness of 20 μm is bonded to the waveguide core region, and is put into a vacuum laminator set at 140 ° C. for thermocompression bonding. Then, 100 mJ was irradiated on the entire surface and heated in a dryer at 120 ° C. for 1 hour to cure Avatrel 2000P to form an upper clad to obtain an optical waveguide. At this time, the upper clad was colorless and transparent, and the refractive index was 1.52.

(Evaluation)
(Evaluation of optical waveguide loss)
Light emitted from an 850 nm VCSEL (surface emitting laser) was introduced into the optical waveguide via a 50 μmφ optical fiber, received by a 200 μmφ optical fiber, and the light intensity was measured. In addition, the cutback method was employ | adopted for the measurement. When the waveguide length is plotted on the horizontal axis and the insertion loss is plotted on the vertical axis, the measured values are neatly arranged on a straight line, and the propagation loss can be calculated as 0.03 dB / cm from the inclination.
(Refractive index difference between core region and cladding region)
The refractive index difference between the left and right core regions adjacent to the horizontal direction—the cladding region (core region and cladding region formed in the above (formation of core region and cladding region)) was determined as follows.
The optical waveguide analyzer was irradiated with laser light having a wavelength of 656 nm by an optical waveguide analyzer OWA-9500 manufactured by EXFO, Canada, and the refractive indexes of the core region and the cladding region were measured, and the difference was calculated. The refractive index difference was 0.02.

(Example 2)
(1) Synthesis of norbornene-based resin having no leaving group In a glove box filled with dry nitrogen in which the water and oxygen concentrations are both controlled to 1 ppm or less, 9.4 g of hexylnorbornene (HxNB) (53. 1 mmol) and 10.5 g (53.1 mmol) of phenylethylnorbornene were weighed into a 500 mL vial, 60 g of dehydrated toluene and 11 g of ethyl acetate were added, and the top was sealed with a silicon sealer.
Next, weigh 2.06 g (3.2 mmol) of Ni catalyst represented by the above chemical formula (B) and 10 mL of dehydrated toluene in a 100 mL vial, put a stirrer chip and seal tightly, and thoroughly stir the catalyst. Dissolved in.
1 mL of Ni catalyst solution represented by the chemical formula (B) is accurately weighed with a syringe, quantitatively injected into the vial containing the above two types of norbornene, and stirred at room temperature for 1 hour. It was done. At this point, the stopper was removed, 60 g of tetrahydrofuran (THF) was added, and the mixture was stirred to obtain a reaction solution.
In a 100 mL beaker, 9.5 g of acetic anhydride, 18 g of hydrogen peroxide (concentration 30%) and 30 g of ion-exchanged water were added and stirred to prepare an aqueous solution of peracetic acid on the spot. Next, the total amount of this aqueous solution was added to the above reaction solution and stirred for 12 hours to reduce Ni.
Next, the treated reaction solution was transferred to a separatory funnel, the lower aqueous layer was removed, and then 100 mL of a 30% aqueous solution of isopropyl alcohol was added and vigorously stirred. The aqueous layer was removed after standing and completely separating the two layers. After repeating this water washing process three times in total, the oil layer was dropped into a large excess of acetone to reprecipitate the polymer produced, separated from the filtrate by filtration, and then in a vacuum dryer set at 60 ° C. Polymer # 2 was obtained by heat drying for 12 hours. The molecular weight distribution of polymer # 2 is Mw = 90,000 by GPC measurement, Mn = 40,000, and the molar ratio of each structural unit in polymer # 2 is 50 mol% hexylbornene structural unit by phenyl identification. The ethyl norbornene structural unit was 50 mol%. The refractive index was 1.54 (measurement wavelength: 633 nm) by Metricon.

(2) Production method of photosensitive resin composition 10 g of the purified polymer # 2 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of an antioxidant Irganox 1076 (manufactured by Ciba Geigy), cyclohexyloxetane monomer (formula) 20 shown by Toa Gosei CHOX, CAS # 483303-3-25-9, molecular weight 186, boiling point 125 ° C./1.33 kPa) 2 g, photoacid generator Rhodorsil Photoinitiator 2074 (manufactured by Rhodia, CAS # 178233-72-2) ) (1.36E-2 g, in 0.1 mL of ethyl acetate) and uniformly dissolved, and then filtered through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V2.

(3) Manufacturing method of optical waveguide film (production of lower clad)
A lower clad similar to that in Example 1 was produced.
(Formation of core region and cladding region)
The photosensitive resin composition varnish V2 was uniformly applied on the lower clad by a doctor blade, and then placed in a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
An upper clad similar to that in Example 1 was produced.

(4) Evaluation Evaluation was performed in the same manner as in Example 1. The propagation loss could be calculated as 0.04 dB / cm. The difference in refractive index between the core region and the cladding region was 0.01.

(Example 3)
(1) Synthesis of norbornene-based resin having a leaving group A norbornene-based resin was produced in the same manner as in Example 1.
(2) Production method of photosensitive resin composition 10 g of the purified polymer # 1 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of antioxidant Irganox 1076 (manufactured by Ciba Geigy) 0.01 g of bifunctional oxetane monomer ( Formula (15), Toa Gosei, DOX, CAS # 18934-00-4, molecular weight 214, boiling point 119 ° C./0.67 kPa) 2 g, photoacid generator Rhodosil Photoinitiator 2074 (Rhodia, CAS # 178233) -72-2) (1.36E-2 g in 0.1 mL of ethyl acetate) was added and dissolved uniformly, and then filtered through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V3. .

(3) Manufacturing method of optical waveguide film (production of lower clad)
A lower clad similar to that in Example 1 was produced.
(Formation of core region and cladding region)
After the photosensitive resin composition varnish V3 was uniformly applied on the lower clad by a doctor blade, it was put into a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
An upper clad similar to that of Example 1 was produced.

(4) Evaluation Evaluation was performed in the same manner as in Example 1. The propagation loss could be calculated as 0.04 dB / cm. The difference in refractive index between the core region and the cladding region was 0.01.

Example 4
(1) Synthesis of norbornene-based resin having a leaving group A norbornene-based resin was produced in the same manner as in Example 1.
(2) Method for Producing Photosensitive Resin Composition 10 g of the purified polymer # 1 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of an antioxidant Irganox 1076 (manufactured by Ciba Geigy), alicyclic epoxy monomer (Shown by the formula (37), manufactured by Daicel Chemical Industries, Celoxide 2021P, CAS # 2386-87-0, molecular weight 252, boiling point 188 ° C./4 hPa) 2 g, photoacid generator RhodosilPhotoinitiator 2074 (manufactured by Rhodia, CAS # 178233) -72-2) (1.36E-2 g in 0.1 mL of ethyl acetate) was added and dissolved uniformly, and then filtered through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V4. .
(3) Manufacturing method of optical waveguide film (production of lower clad)
A lower clad similar to that in Example 1 was produced.
(Formation of core region and cladding region)
After the photosensitive resin composition varnish V4 was uniformly applied on the lower clad by a doctor blade, it was put into a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
An upper clad similar to that of Example 1 was produced.
(4) Evaluation was performed in the same manner as in Evaluation Example 1. The propagation loss could be calculated as 0.04 dB / cm. The difference in refractive index between the core region and the cladding region was 0.01.

(Example 5)
(1) Synthesis of norbornene-based resin having a leaving group A norbornene-based resin was produced in the same manner as in Example 1.
(2) Production method of photosensitive resin composition 10 g of the purified polymer # 1 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of antioxidant Irganox 1076 (manufactured by Ciba Geigy), cyclohexyl oxetane monomer (formula) 20, 1 g of CHOX manufactured by Toa Gosei, 1 g of alicyclic epoxy monomer (manufactured by Daicel Chemical, Celoxide 2021P), photoacid generator Rhodorsil Photoinitiator 2074 (manufactured by Rhodia, CAS # 178233-72-2) (1.36E) -2 g in 0.1 mL of ethyl acetate) and uniformly dissolved, followed by filtration through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V5.
(3) Manufacturing method of optical waveguide film (production of lower clad)
A lower clad similar to that in Example 1 was produced.
(Formation of core region and cladding region)
After the photosensitive resin composition varnish V5 was uniformly applied on the lower clad by a doctor blade, it was put into a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
An upper clad similar to that of Example 1 was produced.
(4) Evaluation Evaluation was performed in the same manner as in Example 1. The propagation loss could be calculated as 0.03 dB / cm. The difference in refractive index between the core region and the cladding region was 0.01.

(Example 6)
(1) Synthesis of norbornene-based resin having a leaving group A norbornene-based resin was produced in the same manner as in Example 1.
(2) Production method of photosensitive resin composition 10 g of the purified polymer # 1 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of antioxidant Irganox 1076 (manufactured by Ciba Geigy), cyclohexyl oxetane monomer (formula) 1.5, CHO (produced by Toa Gosei Co., Ltd.), photoacid generator Rhodorsil Photoinitiator 2074 (manufactured by Rhodia, CAS # 178233-72-2) (1.36E-2 g, in 0.1 mL of ethyl acetate) was added uniformly. Then, it was filtered through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V6.
(3) Manufacturing method of optical waveguide film (production of lower clad)
A lower clad similar to that in Example 1 was produced.
(Formation of core region and cladding region)
After the photosensitive resin composition varnish V6 was uniformly applied on the lower clad by a doctor blade, it was put into a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
An upper clad similar to that of Example 1 was produced.
(4) Evaluation was performed in the same manner as in Evaluation Example 1. The propagation loss could be calculated as 0.03 dB / cm. The difference in refractive index between the core region and the cladding region was 0.01.

(Example 7)
(1) Synthesis of norbornene-based resin having a leaving group In a glove box whose water and oxygen concentrations are both controlled to 1 ppm or less and filled with dry nitrogen, 6.4 g (36.1 mmol) of hexylnorbornene (HxNB) ), Diphenylmethylnorbornene methoxysilane (diPhNB) 8.7 g (27.1 mmol) and epoxynorbornene (EpNB) 4.9 g (27.1 mmol) are weighed into a 500 mL vial, 60 g of dehydrated toluene and 11 g of ethyl acetate are added, The top was sealed with a silicon sealer.
Next, 1.75 g (3.2 mmol) of the Ni catalyst represented by the above chemical formula (B) and 10 mL of dehydrated toluene are weighed in a 100 mL vial, put a stirrer chip and sealed, and the catalyst is thoroughly stirred to completely Dissolved in.
When 1 mL of the Ni catalyst solution represented by the above chemical formula (B) is accurately weighed with a syringe, and quantitatively injected into the vial bottle in which the three types of norbornene are dissolved, and stirred at room temperature for 1 hour, a marked increase in viscosity occurs. Was confirmed. At this point, the stopper was removed, 60 g of tetrahydrofuran (THF) was added, and the mixture was stirred to obtain a reaction solution.
In a 100 mL beaker, 9.5 g of acetic anhydride, 18 g of hydrogen peroxide (concentration 30%) and 30 g of ion-exchanged water were added and stirred to prepare an aqueous solution of peracetic acid on the spot. Next, the total amount of this aqueous solution was added to the above reaction solution and stirred for 12 hours to reduce Ni.
Next, the treated reaction solution was transferred to a separatory funnel, the lower aqueous layer was removed, and then 100 mL of a 30% aqueous solution of isopropyl alcohol isopropyl alcohol was added and vigorously stirred. The aqueous layer was removed after standing and completely separating the two layers. After repeating this water washing process three times in total, the oil layer was dropped into a large excess of acetone to reprecipitate the polymer produced, separated from the filtrate by filtration, and then in a vacuum dryer set at 60 ° C. Polymer # 3 was obtained by heat drying for 12 hours. The molecular weight distribution of the polymer # 3 is Mw = 80,000 by GPC measurement, Mn = 40,000, and the molar ratio of each structural unit in the polymer # 3 is 40 mol% hexylbornene structural unit, The methylnorbornene methoxysilane structural unit was 30 mol%, and the epoxy norbornene structural unit was 30 mol%. The refractive index was 1.53 (measurement wavelength: 633 nm) by Metricon.

(2) Production method of photosensitive resin composition 10 g of the purified polymer # 3 was weighed into a 100 mL glass container, and 40 g of mesitylene, 0.01 g of antioxidant Irganox 1076 (manufactured by Ciba Geigy), cyclohexyloxetane monomer (formula) No. 20 (CHOA manufactured by Toa Gosei Co., Ltd.) 1.0 g, photoacid generator Rhodorsil Photoinitiator 2074 (manufactured by Rhodia, CAS # 178233-72-2) (1.36E-2 g, in 0.1 mL of ethyl acetate) was added uniformly. Then, it was filtered through a 0.2 μm PTFE filter to obtain a clean photosensitive resin composition varnish V7.

(3) Manufacturing method of optical waveguide film (production of lower clad)
A lower clad similar to that in Example 1 was produced.
(Formation of core region and cladding region)
After the photosensitive resin composition varnish V7 was uniformly applied on the lower clad by a doctor blade, it was put into a dryer at 45 ° C. for 15 minutes. After completely removing the solvent, a photomask was pressed and selectively irradiated with ultraviolet rays at 500 mJ / cm ² . The mask was removed, and heating was performed in three stages in a dryer at 45 ° C. for 30 minutes, 85 ° C. for 30 minutes, and 150 ° C. for 1 hour. It was confirmed that a very clear waveguide pattern appeared after heating.
(Formation of upper cladding)
An upper clad similar to that of Example 1 was produced.
(4) Evaluation Evaluation was performed in the same manner as in Example 1. The propagation loss could be calculated as 0.04 dB / cm. The difference in refractive index between the core region and the cladding region was 0.02.

In Examples 1 to 7, when light is applied to the photosensitive resin composition, an acid is generated from the photoacid generator, and a monomer having a cyclic ether group is polymerized only in the irradiated portion. Then, since the amount of unreacted monomer in the irradiated part decreases, the monomer in the unirradiated part diffuses into the irradiated part in order to eliminate the concentration gradient generated between the irradiated part / unirradiated part.
Further, when heating is performed after light irradiation, the monomer volatilizes from the unirradiated portion.
As described above, the monomer-derived structure concentration differs between the core region and the clad region, and in the clad region, the structure derived from the monomer having a cyclic ether group increases, and in the core region, the monomer having a cyclic ether group. It can be seen that the derived structure is reduced.
In Examples 1 to 7, a linear optical waveguide is formed. However, when a curved optical waveguide (with a radius of curvature of about 10 mm) is formed, it is remarkable that optical loss is small.
Furthermore, the optical waveguide films obtained in Examples 1 to 7 have high heat resistance and have reflow resistance of 260 ° C.
Hereinafter, examples of the reference form will be added.
1. (A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
A photosensitive resin composition comprising:
2.1. In the photosensitive resin composition described in
A photosensitive resin composition for an optical waveguide.
3.1. Or 2. In the photosensitive resin composition described in
The photosensitive resin composition whose said cyclic ether group of said (B) is an oxetanyl group or an epoxy group.
4.1. To 3. In the photosensitive resin composition according to any one of
The photosensitive resin composition wherein (A) is a norbornene resin.
5.1. To 4. In the photosensitive resin composition according to any one of
(B) has a lower refractive index than (A),
The cyclic olefin resin is desorbed by an acid generated from the photoacid generator (C), and a photosensitive resin composition having a leaving group that lowers the refractive index of the resin (A) by desorption. .
6). (A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
Having a layer made of a cured product obtained by curing
The layer has a core region and a pair of clad regions that are disposed across the core region and are adjacent to the core region,
The refractive index of the core region is higher than the refractive index of the cladding region,
An optical waveguide film in which the structure concentration derived from (B) in the core region is different from the structure concentration derived from (B) in the cladding region.
7.6. In the optical waveguide film described in
An optical waveguide film in which a difference in refractive index between the core region and the cladding region is 0.01 or more.
8.6. Or 7. In the optical waveguide film described in
Said (A) is an optical waveguide film which is a norbornene-type resin.
9.6. To 8. In the optical waveguide film according to any one of
The optical waveguide film wherein the cyclic ether group (B) is an oxetanyl group or an epoxy group.
10.6. To 9. In the optical waveguide film according to any one of
An optical waveguide film having another pair of cladding regions arranged so as to sandwich the core region from a direction different from the pair of cladding regions.
11. (A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
An optical waveguide film in which a region irradiated with light is one of a cladding region and a core region, and an unirradiated region is the other of the cladding region and the core region.
12 (A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
A process of selectively irradiating light to a photosensitive resin composition comprising:
Heating the sensitive resin composition,
A method for producing an optical waveguide film, wherein a region irradiated with light is one of a cladding region and a core region, and an unirradiated region is the other of a cladding region and a core region.

DESCRIPTION OF SYMBOLS 1 Varnish 2 Base material 3 Optical waveguide film 11 Optical waveguide formation film 111 Clad area | region 112 Core area | region M Mask

Claims (2)

(A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
Include, it is those before Symbol monomer and the oligomer is polymerized by ring opening in the presence of an acid, and photosensitive property of the by acid generated from the (C) by irradiation with light (B) is polymerized An optical waveguide film in which a region irradiated with light is a cladding region and an unirradiated region is a core region. (A) a cyclic olefin resin;
(B) The refractive index is different from that of (A), and at least one of a monomer having a cyclic ether group and an oligomer having a cyclic ether group;
(C) a photoacid generator;
A photosensitive resin composition in which the monomer and the oligomer are polymerized by ring-opening in the presence of an acid, by selectively irradiating light to generate an acid from (C), A step of polymerizing (B) ;
Heating the photosensitive resin composition,
A method of manufacturing an optical waveguide film in which a region irradiated with light is a cladding region and an unirradiated region is a core region.

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