Photosensitive resin composition set

Abstract

Provided is a photosensitive resin composition set capable of producing a single-mode optical waveguide having little change in optical transmission loss before and after a reliability test. The photosensitive resin composition set comprises a core resin composition and a coating resin composition, and the core resin composition and the coating resin composition respectively comprise: (A) a resin (a1) containing a carboxyl group or a resin (a2) containing an epoxy group and a radically polymerizable group; (B) an epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, at least the coating resin composition further contains (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group, and a (meth) acryloyl group, and the content of component (E) in the core resin composition and the content of component (E) in the coating resin composition satisfy a specific relational expression.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition set, and further to a photosensitive resin sheet set, a photosensitive resin ink set, an optical waveguide, a method for producing an optical waveguide, an optoelectronic hybrid substrate, and a method for producing an optoelectronic hybrid substrate. Background Art

[0002] With the advancement of technologies such as 5G communications, autonomous driving, IoT, artificial intelligence, and big data, the demand for ultra-high-speed and large-capacity communications is increasing. The semiconductor packaging that supports its foundation has traditionally responded to high-speed communications by passing high-frequency currents. However, in recent years, the generation of noise, communication losses, and heat generation caused by high-speed communications have become increasingly prominent. In order to solve these problems, in recent years, attempts have been actively made to install optical circuits on electrical wiring substrates to achieve energy saving and low-latency high-speed communications (Patent Documents 1 and 2).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2019-211540;

[0006] Patent document 2: Japanese Patent No. 5771978. Summary of the invention

[0007] Problems to be solved by the invention

[0008] In particular, research on the introduction of silicon photonics is being actively conducted in data centers that require high-speed transmission. Silicon photonics is highly compatible with conventional LSI manufacturing processes. Therefore, it is expected that by effectively utilizing silicon photonics, nanometer-sized fine-line waveguides can be formed at low cost based on the technology cultivated in electronic circuit integration technology.

[0009] For example, according to silicon photonics, it is expected that an optical integrated circuit can be formed on a chip by means of a fine line waveguide. In the case of manufacturing an optoelectronic hybrid substrate equipped with the chip, in order to take out the signal light from the fine line waveguide in the chip to the outside of the chip and connect it to the wiring between the chips, it is required to set an optical waveguide on the optoelectronic hybrid substrate. From the viewpoint of efficiently forming a fine optical waveguide, it is hoped that the optical waveguide is formed by a cured product of a photosensitive resin composition. Since the optoelectronic hybrid substrate requires the same reliability as a printed substrate, it is hoped that the change in optical transmission loss is small before and after reliability tests such as a moisture and heat resistance test (HAST test) or a heat resistance test (reflow test). In addition, from the viewpoint of high-speed transmission, the optical waveguide used in the optoelectronic hybrid circuit is preferably a single-mode optical waveguide.

[0010] Means for solving problems

[0011] The present invention is proposed in view of the above-mentioned problems, and its purpose is to provide: a photosensitive resin composition set that can produce a single-mode optical waveguide with a small change in light transmission loss before and after a reliability test; a photosensitive resin sheet set; a photosensitive resin ink set; an optical waveguide; a method for producing the optical waveguide; an optoelectronic hybrid substrate having the optical waveguide; and a method for producing the optoelectronic hybrid substrate.

[0012] That is, the present invention includes the following contents.

[0013] <1> A photosensitive resin composition set comprising a core resin composition and a coating resin composition,

[0014] The core resin composition and the covering resin composition respectively contain:

[0015] (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group;

[0016] (B) Epoxy resin;

[0017] (C) a photocurable resin; and

[0018] (D) a photopolymerization initiator,

[0019] At least the coating resin composition further comprises:

[0020] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0021] When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship:

[0022] 0.6≤(E)clad-(E)core≤10.

[0023] <2> The photosensitive resin composition set described in <1>, wherein the resin (a1) comprises at least one of an aralkyl type resin and a Cardo type resin.

[0024] <3> The photosensitive resin composition set according to <1>, wherein the resin (a2) contains a (meth)acryloyl group.

[0025] <4> The photosensitive resin composition set according to any one of <1> to <3>, wherein (E) clad is 1 to 12% by mass.

[0026] <5> The photosensitive resin composition set according to any one of <1> to <4>, wherein, when the content of the component (C) in the core resin composition when the non-volatile component of the core resin composition is 100% by mass is (C)core, and the content of the component (C) in the coating resin composition when the non-volatile component of the coating resin composition is 100% by mass is (C)clad, (C)core and (C)clad satisfy the following relationship:

[0027] 0.9≤(C)clad / (C)core≤1.5.

[0028] <6> The photosensitive resin composition set according to any one of <1> to <5>, wherein, when the contents of the component (A) and the component (B) in the core resin composition when the non-volatile component of the core resin composition is 100% by mass are denoted as (A)core and (B)core, respectively, (A)core and (B)core satisfy the following relationship:

[0029] 0.1≤(A)core / (B)core≤5.

[0030] <7> The photosensitive resin composition set according to any one of <1> to <6>, wherein when the contents of the component (A) and the component (B) in the coating resin composition when the non-volatile component of the coating resin composition is 100% by mass are represented by (A)clad and (B)clad, respectively, (A)clad and (B)clad satisfy the following relationship:

[0031] 0.1≤(A)clad / (B)clad≤5.

[0032] <8> The photosensitive resin composition set according to any one of <1> to <7>, wherein, when the contents of the component (A) and the component (C) in the core resin composition when the non-volatile component of the core resin composition is 100% by mass are denoted as (A)core and (C)core, respectively, (A)core and (C)core satisfy the following relationship:

[0033] 0.1≤(A)core / (C)core≤5.

[0034] <9> The photosensitive resin composition set according to any one of <1> to <8>, wherein when the contents of the component (A) and the component (C) in the coating resin composition when the non-volatile component of the coating resin composition is 100% by mass are represented by (A)clad and (C)clad, respectively, (A)clad and (C)clad satisfy the following relationship:

[0035] 0.1≤(A)clad / (C)clad≤5.

[0036] <10> The photosensitive resin composition set according to any one of <1> to <9>, wherein each of the core resin composition and the coating resin composition further contains (H) an organic solvent.

[0037] <11> The photosensitive resin composition kit according to any one of <1> to <10>, which is a photosensitive resin composition kit for producing an optical waveguide.

[0038] <12> The photosensitive resin composition kit according to any one of <1> to <11>, which is a photosensitive resin composition kit for producing an optical waveguide capable of transmitting light having a wavelength of 1300 nm to 1320 nm.

[0039] <13> The photosensitive resin composition kit according to any one of <1> to <12>, which is a photosensitive resin composition kit for producing a single-mode optical waveguide.

[0040] <14> A photosensitive resin sheet set comprising a core resin sheet and a covering resin sheet,

[0041] The core resin sheet comprises: a resin composition layer including the core resin composition in the photosensitive resin composition set according to any one of <1> to <13>,

[0042] The coating resin sheet includes a resin composition layer containing the coating resin composition in the photosensitive resin composition set according to any one of <1> to <13>.

[0043] <15> A photosensitive resin ink set comprising a core resin ink and a coating resin ink,

[0044] The core resin ink comprises: the core resin composition in the photosensitive resin composition set described in any one of <1> to <13>,

[0045] The coating resin ink includes the coating resin composition in the photosensitive resin composition set according to any one of <1> to <13>.

[0046] <16> An optical waveguide comprising a core layer and a cladding layer,

[0047] The core layer comprises a cured product of a core resin composition, wherein the core resin composition comprises:

[0048] (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group;

[0049] (B) Epoxy resin;

[0050] (C) a photocurable resin; and

[0051] (D) a photopolymerization initiator,

[0052] May also include:

[0053] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0054] The coating layer comprises a cured product of a coating resin composition, wherein the coating resin composition comprises:

[0055] (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group;

[0056] (B) Epoxy resin;

[0057] (C) a photocurable resin;

[0058] (D) a photopolymerization initiator; and

[0059] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0060] When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship:

[0061] 0.6≤(E)clad-(E)core≤10.

[0062] <17> An optoelectronic hybrid substrate comprising the optical waveguide described in <16>.

[0063] <18> A method for producing an optical waveguide, the method comprising the following steps in order:

[0064] A step of forming a first composition layer including a coating resin composition;

[0065] a step of curing the first composition layer;

[0066] forming a second composition layer including a core resin composition on the first composition layer;

[0067] A step of subjecting the second composition layer to an exposure treatment;

[0068] A step of developing the second composition layer;

[0069] a step of curing the second composition layer;

[0070] forming a third composition layer including a coating resin composition on the second composition layer; and

[0071] a step of curing the third composition layer,

[0072] The core resin composition and the covering resin composition respectively contain:

[0073] (A) a carboxyl group-containing resin (a1);

[0074] (B) Epoxy resin;

[0075] (C) a photocurable resin; and

[0076] (D) a photopolymerization initiator,

[0077] At least the coating resin composition further comprises:

[0078] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0079] When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship:

[0080] 0.6≤(E)clad-(E)core≤10.

[0081] <19> A method for producing an optical waveguide, the method comprising the following steps in order:

[0082] A step of forming a first composition layer including a coating resin composition;

[0083] a step of curing the first composition layer;

[0084] forming a second composition layer including a core resin composition on the first composition layer;

[0085] a step of curing the second composition layer;

[0086] forming a fourth composition layer including a resist composition on the second composition layer;

[0087] A step of subjecting the fourth composition layer to an exposure treatment;

[0088] A step of developing the fourth composition layer;

[0089] forming a pattern on the second composition layer;

[0090] forming a third composition layer including a coating resin composition on the second composition layer; and

[0091] a step of curing the third composition layer,

[0092] The core resin composition and the covering resin composition respectively contain:

[0093] (A) a resin (a2) containing an epoxy group and a free radical polymerizable group;

[0094] (B) Epoxy resin;

[0095] (C) a photocurable resin; and

[0096] (D) a photopolymerization initiator,

[0097] At least the coating resin composition further comprises:

[0098] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0099] When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship:

[0100] 0.6≤(E)clad-(E)core≤10.

[0101] <20> A method for manufacturing an optoelectronic hybrid substrate, the method comprising the following steps in sequence:

[0102] A step of forming a first composition layer including a coating resin composition;

[0103] a step of curing the first composition layer;

[0104] forming a second composition layer including a core resin composition on the first composition layer;

[0105] A step of subjecting the second composition layer to an exposure treatment;

[0106] A step of developing the second composition layer;

[0107] a step of curing the second composition layer;

[0108] forming a third composition layer including a coating resin composition on the second composition layer; and

[0109] a step of curing the third composition layer,

[0110] The core resin composition and the covering resin composition respectively contain:

[0111] (A) a carboxyl group-containing resin (a1);

[0112] (B) Epoxy resin;

[0113] (C) a photocurable resin; and

[0114] (D) a photopolymerization initiator,

[0115] At least the coating resin composition further comprises:

[0116] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0117] When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship:

[0118] 0.6≤(E)clad-(E)core≤10.

[0119] <21> A method for manufacturing an optoelectronic hybrid substrate, the method comprising the following steps in sequence:

[0120] A step of forming a first composition layer including a coating resin composition;

[0121] a step of curing the first composition layer;

[0122] forming a second composition layer including a core resin composition on the first composition layer;

[0123] a step of curing the second composition layer;

[0124] forming a fourth composition layer including a resist composition on the second composition layer;

[0125] A step of subjecting the fourth composition layer to an exposure treatment;

[0126] A step of developing the fourth composition layer;

[0127] forming a pattern on the second composition layer;

[0128] forming a third composition layer including a coating resin composition on the second composition layer; and

[0129] a step of curing the third composition layer,

[0130] The core resin composition and the covering resin composition respectively contain:

[0131] (A) a resin (a2) containing an epoxy group and a free radical polymerizable group;

[0132] (B) Epoxy resin;

[0133] (C) a photocurable resin; and

[0134] (D) a photopolymerization initiator,

[0135] At least the coating resin composition further comprises:

[0136] (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group,

[0137] When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship:

[0138] 0.6≤(E)clad-(E)core≤10.

[0139] Effects of the Invention

[0140] According to the present invention, there can be provided: a photosensitive resin composition set capable of manufacturing a single-mode optical waveguide with a small change in light transmission loss before and after a reliability test; a photosensitive resin sheet set; a photosensitive resin ink set; an optical waveguide; a method for manufacturing the optical waveguide; an optoelectronic hybrid substrate having the optical waveguide; and a method for manufacturing the optoelectronic hybrid substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0141] [ Figure 1 ] Figure 1 It is a perspective view schematically showing an optical waveguide according to one embodiment of the present invention.

[0142] [ Figure 2 ] Figure 2 This is a schematic cross-sectional view for explaining step (I) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0143] [ Figure 3 ] Figure 3 This is a schematic cross-sectional view for explaining step (II) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0144] [ Figure 4 ] Figure 4 This is a schematic cross-sectional view for explaining step (III) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0145] [ Figure 5 ] Figure 5 This is a schematic cross-sectional view for explaining step (IV) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0146] [ Figure 6 ] Figure 6 This is a schematic cross-sectional view for explaining step (V) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0147] [ Figure 7 ] Figure 7 This is a schematic cross-sectional view for explaining step (VI) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0148] [ Figure 8 ] Figure 8 This is a schematic cross-sectional view for explaining step (VII) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0149] [ Fig. 9 ] Fig. 9 This is a schematic cross-sectional view for explaining step (VIII) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention.

[0150] [ Fig.10 ] Fig.10 This is a schematic cross-sectional view for explaining step (IX) of the method for manufacturing the optical waveguide according to the first embodiment of the present invention. DETAILED DESCRIPTION

[0151] <Explanation of terms>

[0152] In this specification, the term "organic group" refers to a group containing at least carbon atoms as backbone atoms, which may be any of linear, branched or cyclic. In this specification, unless otherwise specified, the number of backbone atoms of the organic group is preferably 1 to 50, more preferably 1 to 30, and more preferably 1 to 20 or 1 to 10. The number of backbone atoms does not include the number of backbone atoms of the epoxy group. Examples of organic groups include: groups consisting of one or more backbone atoms (including at least carbon atoms) selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms.

[0153] In this specification, the term "aliphatic group" refers to a group obtained by removing one or more hydrogen atoms from an aliphatic compound. Specifically, an n-valent aliphatic group (here, n represents an integer greater than 1, and the same applies hereinafter) refers to a group obtained by removing n hydrogen atoms from an aliphatic compound. Here, the aliphatic compound may be an aliphatic compound containing no heteroatoms and consisting only of carbon atoms and hydrogen atoms, or may be an aliphatic compound containing heteroatoms and consisting of heteroatoms in addition to carbon atoms and hydrogen atoms. In this specification, the term "heteroatom" refers to an atom other than carbon atoms and hydrogen atoms, and examples thereof include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, halogen atoms, and the like.

[0154] In this specification, the term "aliphatic hydrocarbon group" refers to a group obtained by removing one or more hydrogen atoms from an aliphatic compound containing no heteroatoms and consisting only of carbon atoms and hydrogen atoms. Specifically, an n-valent aliphatic hydrocarbon group refers to a group obtained by removing n hydrogen atoms from an aliphatic compound containing no heteroatoms. Examples of n-valent aliphatic hydrocarbon groups include groups obtained by removing n hydrogen atoms from an aliphatic compound selected from the following: alkanes which may have a substituent, alkenes which may have a substituent, alkynes which may have a substituent, and alkapolyenes which may have a substituent (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and further preferably 2). Here, alkanes, alkenes, alkynes, and alkapolyenes may be either linear or branched, and may also contain a cyclic structure. In this specification, unless otherwise specified, the number of carbon atoms in an aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more or 3 or more, preferably 100 or less, more preferably 80 or less, further preferably 60 or less, 50 or less or 40 or less. The number of carbon atoms does not include the number of carbon atoms of a substituent.

[0155] In this specification, the term "aliphatic group containing heteroatoms" refers to a group obtained by removing one or more hydrogen atoms from an aliphatic compound containing heteroatoms. Specifically, an n-valent aliphatic group containing heteroatoms refers to a group obtained by removing n hydrogen atoms from an aliphatic compound containing heteroatoms. In the "aliphatic group containing heteroatoms" in this specification, the heteroatom can be bonded to any of the carbon atoms constituting the group, for example, (i) it can be bonded to the terminal carbon, and (ii) it can be between carbon-carbon bonds. In addition, in the "aliphatic group containing heteroatoms" in this specification, the bond can extend from the carbon atom or from the heteroatom. The aliphatic group containing heteroatoms can be any saturated or unsaturated aliphatic group containing heteroatoms, and can also have a cyclic structure. As an n-valent heteroatom-containing aliphatic group, for example, there can be mentioned a group obtained by removing n hydrogen atoms from the following heteroatom-containing aliphatic compounds: heteroalkanes which may have a substituent, heteroalkenes which may have a substituent, heteroalkynes which may have a substituent, and heteroalkanes which may have a substituent. Here, the heteroalkanes, heteroalkenes, heteroalkynes, and heteroalkanes may all be straight-chain or branched, and may also contain a cyclic structure. In the heteroatom-containing aliphatic group, the heteroatom is preferably one or more selected from oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms. For example, it may exist as a heteroatom in the form of -O-, -S-, or -N<, or it may exist in the form of -C(=O)-, -S(=O)-, or -S(=O)-. 2 -、-N(R')-、-Si(R') 2- or their combination, or their combination with -O-, -S- exists as a heteroatom-containing group (wherein, R' represents a hydrogen atom or a substituent described later, the same below). In the case where the heteroatom-containing aliphatic group contains more than two heteroatoms, they may be the same as or different from each other. In this specification, unless otherwise specified, the number of heteroatoms in the heteroatom-containing aliphatic group is preferably more than 1, more than 2 or more than 3, preferably less than 30, less than 25 or less than 20. In addition, unless otherwise specified, the number of carbon atoms is preferably more than 1, more preferably more than 2 or more than 3, preferably less than 100, more preferably less than 80, and further preferably less than 60, less than 50 or less than 40. The number of heteroatoms or carbon atoms does not include the number of heteroatoms or carbon atoms of the substituent.

[0156] In this specification, the term "aromatic group" refers to a group after removing one or more hydrogen atoms from an aromatic compound. Specifically, an n-valent aromatic group refers to a group after removing n hydrogen atoms from an aromatic compound. Here, the aromatic compound may be an aromatic compound containing no heteroatoms consisting only of carbon atoms and hydrogen atoms, or an aromatic compound containing heteroatoms consisting of heteroatoms in addition to carbon atoms and hydrogen atoms. In this specification, the term "aromatic compound" refers to a compound containing an aromatic ring. In addition, in this specification, the term "aromatic ring" refers to a ring that follows the Huckel rule and has 4p+2 (p is a natural number) electrons contained in the π electron system on the ring, including a monocyclic aromatic ring and a condensed polycyclic aromatic ring formed by condensing more than two monocyclic aromatic rings. The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring atoms, or may be an aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring atoms in addition to carbon atoms. In this specification, unless otherwise specified, the number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, and further preferably 6 or more, and the upper limit is preferably 24 or less, more preferably 18 or less or 14 or less, and further preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0157] In this specification, the term "aromatic hydrocarbon group" refers to a group obtained by removing one or more hydrogen atoms from an aromatic compound containing no heteroatoms and consisting only of carbon atoms and hydrogen atoms. Specifically, an n-valent aromatic hydrocarbon group refers to a group obtained by removing n hydrogen atoms from an aromatic compound containing no heteroatoms. In this specification, unless otherwise specified, the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 or more, preferably 100 or less, more preferably 80 or less, and further preferably 60 or less, 50 or less, or 40 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0158] In this specification, the term "heteroatom-containing aromatic group" refers to a group obtained by removing one or more hydrogen atoms from an aromatic compound containing heteroatoms. Specifically, an n-valent heteroatom-containing aromatic group refers to a group obtained by removing n hydrogen atoms from an aromatic compound containing heteroatoms. In the "heteroatom-containing aromatic group" in this specification, the heteroatom can be bonded to any of the carbon atoms constituting the group, for example, (i) it can be bonded to the terminal carbon, and (ii) it can be between carbon-carbon bonds. In addition, in the "heteroatom-containing aromatic group" in this specification, the bond can extend from a carbon atom or from a heteroatom. As an n-valent heteroatom-containing aromatic group, for example, a group obtained by removing n hydrogen atoms from a heteroaryl compound that may have a substituent can be cited. In this specification, unless otherwise specified, the number of heteroatoms of the heteroatom-containing aromatic group is preferably 1 or more, 2 or more, or 3 or more, preferably 30 or less, 25 or less, or 20 or less, and unless otherwise specified, the number of carbon atoms is preferably 3 or more, 4 or more, 5 or more, or 6 or more, preferably 100 or less, more preferably 80 or less, and further preferably 60 or less, 50 or less, or 40 or less. The number of heteroatoms or carbon atoms does not include the number of heteroatoms or carbon atoms of the substituent.

[0159] In the present specification, the term "may have a substituent" with respect to a compound or a group means both the case where hydrogen atoms of the compound or group are not substituted with a substituent and the case where part or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0160] In the present specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkapolyenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, an alkenyloxy group, a cycloalkyloxy group, a cycloalkenyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, a monovalent aliphatic heterocyclic group, an alkylene group, an acyl group, an acyloxy group, an amino group, a silyl group, a carboxyl group (carboxy), a sulfo group, a cyano group, a nitro group, a mercapto group and an oxo group.

[0161] Examples of the halogen atom used as a substituent include fluorine, chlorine, bromine and iodine atoms. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The alkenyl or alkynyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkenyl or alkynyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The alkoxy polyenyl group used as a substituent may be either linear or branched, and the number of double bonds is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2. The number of carbon atoms of the alkoxy polyenyl group is preferably 3 to 20, more preferably 3 to 14, even more preferably 3 to 12, and even more preferably 3 to 6. The number of carbon atoms of the cycloalkyl or cycloalkenyl group used as a substituent is preferably 3 to 12, and even more preferably 3 to 6. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6. The alkenyloxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkenyloxy group is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms of the cycloalkyloxy group or cycloalkenyloxy group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The alkylthio group used as a substituent may be either linear or branched. The number of carbon atoms of the alkylthio group is preferably 1 to 12, more preferably 1 to 6. The number of carbon atoms of the cycloalkylthio group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the arylthio group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The monovalent aliphatic heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from an aliphatic heterocyclic compound. The number of carbon atoms of the monovalent aliphatic heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The alkylene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The acyl group used as a substituent refers to a group of the formula: -C(=O)-R S The group represented by (wherein R S is an alkyl group). S The alkyl group represented may be straight chain or branched. The number of carbon atoms in the acyl group is preferably 2 to 13, more preferably 2 to 7. The acyloxy group used as a substituent is of the formula: -OC(=O)-R S The group represented by (wherein RS The acyloxy group preferably has 2 to 13 carbon atoms, and more preferably 2 to 7 carbon atoms. The above substituents may further have substituents (sometimes referred to as "secondary substituents"). As secondary substituents, the same substituents as those described above may be used unless otherwise specified.

[0162] In this specification, the term "C p ~C q "(p and q are positive integers, and p < q) means that the number of carbon atoms in the organic group recorded immediately after the term is p to q. For example, "C 1 ~C 6 "Alkyl" means an alkyl group having 1 to 6 carbon atoms. 6 ~C 10 The term "cycloalkyl group" refers to a cycloalkyl group having 6 to 10 carbon atoms.

[0163] In the present specification, the term "(meth)acrylic acid" includes acrylic acid, methacrylic acid and a combination thereof, the term "(meth)acryloyl" includes acrylyl, methacryloyl and a combination thereof, and the term "(meth)acrylate" includes acrylate, methacrylate and a combination thereof.

[0164] Hereinafter, the present invention will be described in detail by way of embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0165] [Photosensitive resin composition kit]

[0166] The photosensitive resin composition kit of the present invention comprises a core resin composition and a coating resin composition. The core resin composition can be suitably used as a photosensitive resin composition for forming a core layer of an optical waveguide, and the coating resin composition can be suitably used as a photosensitive resin composition for forming a coating layer of an optical waveguide. The photosensitive resin composition kit of the present invention can be used for the production of an optical waveguide comprising: a core layer comprising a cured product of the core resin composition and a coating layer comprising a cured product of the coating resin composition.

[0167] In the photosensitive resin composition kit of the present invention,

[0168] The core resin composition and the covering resin composition respectively contain:

[0169] (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group;

[0170] (B) Epoxy resin;

[0171] (C) a photocurable resin; and

[0172] (D) a photopolymerization initiator,

[0173] At least the coating resin composition further comprises:

[0174] (E) An alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group, and a (meth)acryloyl group.

[0175] Furthermore, the photosensitive resin composition set of the present invention is characterized in that, when the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is set to 100 mass % is set to (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is set to 100 mass % is set to (E)clad, (E)core and (E)clad satisfy the relationship of 0.6≤(E)clad-(E)core≤10.

[0176] According to the photosensitive resin composition kit of the present invention, a single-mode optical waveguide having a small change in optical transmission loss before and after a reliability test can be manufactured. In addition, according to the photosensitive resin composition kit of the present invention, an optical waveguide having a small value of optical transmission loss even after a reliability test can be manufactured. Furthermore, the photosensitive resin composition kit of the present invention can generally achieve good fine-line waveguide formability.

[0177] As described above, the core resin composition and the coating resin composition respectively contain: (A) a carboxyl-containing resin (a1), or a resin (a2) containing an epoxy group and a free radical polymerizable group; (B) an epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, and at least the coating resin composition further contains: (E) an alkoxysilane compound having one or more functional groups selected from epoxy, phenylamino, vinyl and (meth)acryloyl groups. Moreover, the core resin composition and the coating resin composition contain each component to satisfy the relationship of 0.6≤(E)clad-(E)core≤10. The core resin composition and the coating resin composition may also contain optional components such as (F) a curing accelerator, (G) other additives and (H) an organic solvent as needed. In the following, the core resin composition and the coating resin composition are sometimes collectively referred to as "resin composition".

[0178] <(A) Carboxyl-containing resin (a1) or epoxy- and radically polymerizable-group-containing resin (a2)>

[0179] In the photosensitive resin composition kit of the present invention, the resin composition contains a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a radical polymerizable group as the component (A).

[0180] In the present specification, the carboxyl group-containing resin (a1) as the component (A) may be simply referred to as "resin (a1)" or "component (a1)", and the epoxy group- and radical polymerizable group-containing resin (a2) as the component (A) may be simply referred to as "resin (a2)" or "component (a2)".

[0181] -Carboxyl-containing resin (a1)-

[0182] In one embodiment, the resin composition in the photosensitive resin composition kit of the present invention contains a carboxyl group-containing resin (a1) as component (A). Component (a1) may be used alone or in combination of two or more.

[0183] The resin composition containing the component (a1) is soluble in an alkaline developer (eg, a 1 mass % sodium carbonate aqueous solution) and can be developed with an alkali. The number of carboxyl groups per molecule of the component (a1) may be one or two or more.

[0184] The component (a1) is not limited as long as it can be alkali developed, and preferably further contains a radical polymerizable group. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; and α,β-unsaturated carbonyl groups such as (meth)acryloyl and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl).

[0185] When the component (a1) contains a radical polymerizable group, photo-radical polymerization can be performed. Among them, from the viewpoint of the reactivity of photo-radical polymerization, the component (a1) preferably contains a (meth)acryloyl group. The number of radical polymerizable groups in each molecule of the component (a1) may be 1 or more than 2. In addition, when each molecule of the component (a1) contains more than 2 radical polymerizable groups, these radical polymerizable groups may be the same or different.

[0186] The component (a1) has both a radical polymerizable group and a carboxyl group, and is preferably a resin that can be photo-radical polymerized and can be alkali-developed.

[0187] In one embodiment, the component (a1) preferably comprises an aromatic skeleton. Here, the aromatic skeleton refers to a skeleton comprising an aromatic group, and the aromatic group is as described above. Among them, from the viewpoint of being able to enjoy the effect of the present invention more, the aromatic skeleton more preferably comprises one or more aromatic skeletons selected from an aralkyl skeleton and a Cardo skeleton. That is, in one embodiment, the component (a1) comprises any one or more of an aralkyl type resin and a Cardo type resin.

[0188] Examples of the aralkyl skeleton include a naphthol aralkyl skeleton, a phenol aralkyl skeleton, and a biphenyl aralkyl skeleton, and the aralkyl skeleton is preferably a naphthol aralkyl skeleton from the viewpoint of achieving a better effect of the present invention. Therefore, in one embodiment, the component (a1) contains a naphthol aralkyl type resin as the aralkyl type resin.

[0189] As shown in the following formula (A1), the Cardo skeleton is a structure that forms a ring structure A 1 There are two ring structures A bonded to one carbon atom of 2 and A 3 The skeleton formed.

[0190]

[0191] In formula (A1),

[0192] Ring structure A 1 represents one or more cyclic structures selected from an aliphatic ring and an aliphatic ring fused with an aromatic ring;

[0193] Ring structure A 2 and A 3 Each independently represents one or more cyclic structures selected from the group consisting of an aliphatic ring, an aromatic ring, and an aliphatic ring condensed with an aromatic ring.

[0194] In formula (A1), the ring structure A 1 represents one or more cyclic structures selected from an aliphatic ring and an aliphatic ring fused with an aromatic ring. 1 It may have a substituent. The aliphatic ring may be an aliphatic carbocyclic ring or an aliphatic heterocyclic ring.

[0195] Examples of the aliphatic ring include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; bicycloalkanes such as adamantane, norbornane, and isobornane; tricycloalkanes such as tricyclodecane; and tetracycloalkanes such as tetracyclodecane.

[0196] Examples of the aliphatic ring fused with the aromatic ring include a fluorene ring and similar structures thereof. The similar structures include a skeleton in which at least one of the two benzene rings in the fluorene ring is substituted with a naphthalene ring or the like, a structure in which one of the two benzene rings in the fluorene ring is removed, a structure in which the number of carbon atoms in the five-membered carbon ring in the fluorene ring is changed, combinations thereof, and structures having substituents.

[0197] In formula (A1), the ring structure A 2 and A 3 Each independently represents one or more cyclic structures selected from an aliphatic ring, an aromatic ring, and an aliphatic ring fused with an aromatic ring. 2 and A 3 It may have a substituent. In the ring structure A 2 and A 3 In the case of an aliphatic ring or an aliphatic ring fused with an aromatic ring, examples of these cyclic structures include: 1 Structures in the same range. Ring structure A 2 and A 3 Each independently is preferably an aromatic ring, more preferably an aromatic ring having 6 to 14 carbon atoms, further preferably an aromatic ring having 6 to 10 carbon atoms (eg, a benzene ring or a naphthalene ring), and further preferably a benzene ring.

[0198] Ring structure A in the Cardo skeleton 1 , A 2 and A 3 The substituents that may be possessed are as described above, and preferably at least one selected from a halogen atom, an alkyl group, an alkoxy group, and an aryl group, and more preferably at least one selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms.

[0199] When the component (a1) contains a cardo skeleton (ie, contains a cardo type resin), the cardo skeleton is preferably a divalent group represented by the following formulae (A2-1) to (A2-3), and more preferably a divalent group represented by formula (A2-1): wherein * represents a bonding site.

[0200]

[0201] In a preferred embodiment, the component (a1) includes an acid-modified epoxy (meth)acrylate resin.

[0202] The acid-modified epoxy (meth)acrylate resin can be produced by acid-modifying the epoxy (meth)acrylate resin by a known method. The epoxy (meth)acrylate resin can be produced, for example, by reacting an epoxy resin with (meth)acrylic acid.

[0203] The epoxy resin used for producing the epoxy (meth) acrylate resin is not particularly limited as long as it is a compound having an epoxy group in the molecule, and examples thereof include: bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin modified to have trifunctional or higher functional groups by reacting epichlorohydrin with bisphenol F epoxy resin, and the like; biphenol epoxy resin, tetramethyl Biphenol type epoxy resins; phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, alkylphenol novolac epoxy resins and other novolac epoxy resins; fluorinated epoxy resins such as bisphenol AF epoxy resins and perfluoroalkyl epoxy resins; naphthalene type epoxy resins, dihydroxynaphthalene type epoxy resins, polyhydroxybinaphthyl epoxy resins, naphthol type epoxy resins, naphthol aralkyl type epoxy resins, binaphthol type epoxy resins, sub- Epoxy resins having a naphthalene skeleton (epoxy resins containing a naphthalene skeleton) such as naphthyl ether epoxy resins, naphthol novolac epoxy resins, and naphthalene epoxy resins obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes; biphenylol epoxy resins; dicyclopentadiene epoxy resins; trisphenol epoxy resins; tert-butyl-catechol epoxy resins; anthracene epoxy resins and other epoxy resins containing a condensed ring skeleton; glycidyl amine epoxy resins; glycidyl ester epoxy resins; biphenyl epoxy resins Resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; epoxy resin containing spiro ring; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin; acrylic resin containing glycidyl group such as poly(meth)acrylate glycidyl ester, copolymer of glycidyl methacrylate and acrylate; fluorene type epoxy resin; epoxy resin containing Cardo skeleton; halogenated epoxy resin, etc.

[0204] The epoxy resin used to make the epoxy (meth) acrylate resin preferably contains an aromatic skeleton. As described above, the aromatic skeleton is preferably selected from one or more of an aralkyl skeleton and a Cardo skeleton. Therefore, in one embodiment, the epoxy resin used to make the epoxy (meth) acrylate resin contains one or more of an epoxy resin containing an aralkyl skeleton (preferably a naphthol aralkyl type epoxy resin) and an epoxy resin containing a Cardo skeleton.

[0205] In one embodiment, the acid-modified epoxy (meth)acrylate resin preferably includes a resin selected from the following: an acid-modified epoxy (meth)acrylate resin obtained by esterifying the hydroxyl group of an epoxy (meth)acrylate resin (hereinafter, also referred to as an "ester-type acid-modified epoxy (meth)acrylate resin") and an acid-modified epoxy (meth)acrylate resin obtained by urethane-modifying the hydroxyl group of an epoxy (meth)acrylate resin (hereinafter, also referred to as a "urethane-type acid-modified epoxy (meth)acrylate resin"), and more preferably includes an ester-type acid-modified epoxy (meth)acrylate resin.

[0206] The ester type acid-modified epoxy (meth)acrylate resin can be produced by, for example, reacting an epoxy (meth)acrylate resin with an acid anhydride. The ester type acid-modified epoxy (meth)acrylate resin may be used alone or in combination of two or more.

[0207] Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride. Any one of these may be used alone, or two or more thereof may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred, and tetrahydrophthalic anhydride is more preferred.

[0208] The acid-modified epoxy (meth) acrylate resin can be synthesized by a known method, or a commercial product can be used. Specific examples of commercial products include: "CCR-1373H" (acid-modified epoxy acrylate containing a cresol novolac skeleton), "ZCR-8001H" (acid-modified epoxy acrylate containing a biphenyl skeleton), "ZCR-1569H" (acid-modified epoxy acrylate containing a biphenyl skeleton), "CCR-1171H" (acid-modified epoxy acrylate containing a cresol novolac skeleton), "ZCR-1797H" (acid-modified epoxy acrylate containing a biphenyl skeleton) manufactured by Nippon Kayaku Co., Ltd.; "ZAR-2000" (acid-modified epoxy acrylate resin containing a bisphenol A skeleton), "ZFR-1797H" (acid-modified epoxy acrylate containing a biphenyl skeleton) manufactured by Nippon Kayaku Co., Ltd. -1491H", "ZFR-1533H" (acid-modified epoxy acrylate resin containing bisphenol F skeleton); "PR-300CP" manufactured by Resonac (cresol novolac type acid-modified epoxy acrylate resin); "CCR-1179" manufactured by Nippon Kayaku Co., Ltd. (epoxy acrylate resin containing cresol novolac skeleton); "WR-301" manufactured by ADEKA (acid-modified epoxy acrylate containing Cardo skeleton); "V-259ME" manufactured by Nippon Steel Chemicals Co., Ltd. (acid-modified epoxy acrylate containing Cardo skeleton); "Ogsol CR-TR1", "Ogsol CR-TR2", "Ogsol CR-TR3", "Ogsol CR-TR4", "Ogsol CR-TR5", "Ogsol CR-TR6" (acid-modified epoxy acrylate containing Cardo skeleton) manufactured by Osaka Gas Chemicals Co., Ltd., etc. These may be used alone or in combination of two or more.

[0209] The urethane acid-modified epoxy (meth)acrylate resin can be produced, for example, by reacting an epoxy (meth)acrylate resin with a diisocyanate compound and a carboxyl group-containing diol compound. The urethane acid-modified epoxy (meth)acrylate resin may be used alone or in combination of two or more.

[0210] Examples of the diisocyanate compound include aromatic diisocyanate compounds such as phenylene diisocyanate, toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, diphenyl diisocyanate, and naphthalene diisocyanate; and aliphatic diisocyanate compounds such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, arylene sulfone ether diisocyanate, allyl nitrile diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane.

[0211] As a carboxyl group-containing diol compound, dimethylol propionic acid, dimethylol butyric acid, dimethylol nonanoic acid, etc. are mentioned, for example.

[0212] The urethane acid-modified epoxy (meth)acrylate resin can be synthesized by a known synthesis method, or a commercial product can be used. As a known synthesis method, for example, the method described in Japanese Patent Publication No. 2016-199719 can be cited. As specific examples of commercial products, "UXE-3024", "UXE-3011", "UXE-3012", "UXE-3024" manufactured by Nippon Kayaku Co., Ltd. can be cited.

[0213] From the viewpoint of improving the alkali developability of the resin composition, the acid value of the component (a1) is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, further preferably 1 mgKOH / g or more, 10 mgKOH / g or more, further preferably 20 mgKOH / g or more, 30 mgKOH / g or more, or 40 mgKOH / g or more, 50 mgKOH / g or more. From the viewpoint of improving insulation reliability, the upper limit of the acid value of the component (a1) is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, or 100 mgKOH / g or less.

[0214] The weight average molecular weight (Mw) of the component (a1) is preferably 500 or more, more preferably 750 or more, and further preferably 900 or more. The upper limit of the Mw of the component (a1) is preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less, 8,000 or less, 6,000 or less, or 5,000 or less. The weight average molecular weight (Mw) is a weight average molecular weight of a polystyrene conversion value measured by gel permeation chromatography (GPC).

[0215] - Resin (a2) containing epoxy group and free radical polymerizable group-

[0216] In one embodiment, the resin composition in the photosensitive resin composition kit of the present invention contains a resin (a2) containing an epoxy group and a radical polymerizable group as component (A). Component (a2) may be used alone or in combination of two or more.

[0217] The component (a2) does not contain a component corresponding to the component (a1). For example, in relation to the component (a1), the component (a2) may not contain a carboxyl group.

[0218] The component (a2) has both an epoxy group and a radical polymerizable group, exhibits thermosetting properties, and can be subjected to photoradical polymerization. Therefore, the resin composition containing the component (a2) exhibits both thermosetting properties and photocuring properties.

[0219] The number of epoxy groups in the component (a2) per molecule may be 1 or 2 or more.

[0220] The number of radical polymerizable groups in each molecule of component (a2) may be 1 or 2 or more. Examples of radical polymerizable groups include unsaturated hydrocarbon groups such as vinyl, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; α,β-unsaturated carbonyl groups such as (meth)acryloyl and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl). In the case where two or more radical polymerizable groups are contained in each molecule of component (a2), these radical polymerizable groups may be the same or different.

[0221] Among them, from the viewpoint of the reactivity of photoradical polymerization, it is preferred that the component (a2) contains a (meth)acryloyl group.

[0222] In the component (a2), the remaining structure (hereinafter also referred to as "residue") after removing the epoxy group and the radical polymerizable group is not particularly limited as long as it is an organic group. For example, in the component (a2) having a total of n epoxy groups and radical polymerizable groups, the residue is an n-valent organic group. As described above, the organic group may be any of an aliphatic group and an aromatic group. From the viewpoint of being able to enjoy the effects of the present invention more, the n-valent organic group is preferably an aromatic group, and more preferably an aromatic group containing a heteroatom.

[0223] Regarding the aromatic group, as described above, from the viewpoint of being able to better enjoy the effects of the present invention, the aromatic ring contained in the aromatic group is preferably an aromatic carbocyclic ring, more preferably an aromatic carbocyclic ring having 6 to 14 carbon atoms (preferably 6 to 10). In addition, the number of carbon atoms in the aromatic group is preferably 10 or more, more preferably 12 or more, 14 or more, 16 or more, or 18 or more, and the upper limit of the number of carbon atoms is preferably 50 or less, more preferably 40 or less or 30 or less.

[0224] In the case where the aromatic group is a heteroatom-containing aromatic group, as described above, from the viewpoint of being able to enjoy the effect of the present invention more, the heteroatom-containing aromatic group preferably contains a heteroatom selected from an oxygen atom and a nitrogen atom, more preferably contains a heteroatom in the form of -O-, -N<, -C(=O)-, or a combination thereof, and further preferably contains a heteroatom in the form of -O-, -C(=O)-, or a combination thereof. The number of heteroatoms in the heteroatom-containing aromatic group is as described above, preferably 2 or more or 3 or more, and the upper limit is preferably 10 or less, 8 or less, or 6 or less.

[0225] Among them, from the viewpoint of enjoying the effect of the present invention more, the component (a2) preferably contains one or more aromatic skeletons selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, a naphthalene skeleton, an aralkyl skeleton, and a cardo skeleton, and more preferably contains one or more aromatic skeletons selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a naphthalene skeleton. Here, the bisphenol skeleton refers to a structure obtained by removing n (n is an integer of 2 or more) hydrogen atoms from various bisphenols such as bisphenol A, bisphenol F, bisphenol AP, bisphenol B, bisphenol C, and bisphenol P. The aralkyl skeleton and the cardo skeleton, including suitable examples thereof, are as described for the component (a1).

[0226] The component (a2) according to a suitable embodiment having a (meth)acryloyl group as a free radical polymerizable group can be produced by reacting an epoxy resin with (meth)acrylic acid. The epoxy resin as a raw material can be appropriately selected and used as described for the component (a1) so as to provide the above-mentioned suitable residue and skeleton.

[0227] The component (a2) can be synthesized by a known method, or a commercially available product can be used. Specific examples of commercially available products include "EBECRYL 3605" (bisphenol A epoxy semiacrylate) manufactured by Daicel Allnex.

[0228] The epoxy equivalent of the component (a2) is preferably 100 g / eq. or more, more preferably 200 g / eq. or more, 300 g / eq. or more, or 400 g / eq. or more, and the upper limit is preferably 2,000 g / eq. or less, 1,500 g / eq. or less, or 1,000 g / eq. or less. The epoxy equivalent is the mass of the resin (a2) per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

[0229] As described above, in the photosensitive resin composition kit of the present invention, the resin composition comprises component (a1) or component (a2) as component (A). The resin composition may comprise component (a1) and component (a2) in combination, preferably comprising either component (a1) or component (a2). For example, the photosensitive resin composition kit of the present invention may comprise: a core resin composition comprising component (a1) as component (A) and a coating resin composition comprising component (a1) as component (A); or, may comprise: a core resin composition comprising component (a2) as component (A) and a coating resin composition comprising component (a2) as component (A). Alternatively, the photosensitive resin composition kit of the present invention may further comprise: a core resin composition comprising component (a1) as component (A) and a coating resin composition comprising component (a2) as component (A); or, may further comprise: a core resin composition comprising component (a2) as component (A) and a coating resin composition comprising component (a1) as component (A).

[0230] In the photosensitive resin composition kit of the present invention, the content of the component (A) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 16% by mass or more, 18% by mass or more, or 20% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, 44% by mass or less, 42% by mass or less, or 40% by mass or less.

[0231] It should be noted that, in the present invention, unless otherwise expressly stated, the content of each component in the core resin composition is the value when the non-volatile component in the core resin composition is set to 100% by mass, and unless otherwise expressly stated, the content of each component in the coating resin composition is the value when the non-volatile component in the coating resin composition is set to 100% by mass. The non-volatile component refers to the entire non-volatile component after removing the solvent in the resin composition.

[0232] <(B) Epoxy resin>

[0233] In the photosensitive resin composition kit of the present invention, the resin composition contains an epoxy resin as the component (B). The component (B) may be used alone or in combination of two or more. It should be noted that the component (B) does not contain a component corresponding to the above-mentioned component (A).

[0234] Examples of the component (B) include bisphenol epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidylester epoxy resins, cresol novolac epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, naphthylene ether epoxy resins, trimethylol epoxy resins, and tetraphenylethane epoxy resins. Bisphenol type epoxy resin refers to epoxy resin having a bisphenol structure, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin. Biphenyl type epoxy resin refers to epoxy resin having a biphenyl structure, and the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, biphenyl type epoxy resin and biphenyl aralkyl type epoxy resin are also included in the biphenyl type epoxy resin.

[0235] The component (B) preferably contains an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and usually 100% by mass or less relative to 100% by mass of the component (B).

[0236] The component (B) includes an epoxy resin that is liquid at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resin”). In the photosensitive resin composition kit of the present invention, the resin composition may contain only a liquid epoxy resin as the component (B), or may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin. It is preferred that it contains only a solid epoxy resin, or contains both a liquid epoxy resin and a solid epoxy resin.

[0237] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0238] As the liquid epoxy resin, preferred are glycyrrhizin type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexanedimethanol type epoxy resin, cyclic aliphatic glycidyl ether and epoxy resin having a butadiene structure.

[0239] Specific examples of liquid epoxy resins include: "EX-992L" manufactured by Nagase ChemteX; "YX7400" manufactured by Mitsubishi Chemical Corporation; "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "828EL", "825", "EPIKOTE 828EL" manufactured by Mitsubishi Chemical Corporation; "850" (bisphenol A-type epoxy resin) manufactured by DIC Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "HP820" (alkylphenol-type epoxy resin) manufactured by DIC Corporation; "630", "630LSD", "604" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" manufactured by ADEKA (liquiritiol type epoxy resin); "EP-3950L" and "EP-3980S" manufactured by ADEKA (glycidylamine type epoxy resin); "EP-4088S" manufactured by ADEKA (dicyclopentadiene type epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical Materials Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase "EX-721" manufactured by ChemteX (glycidyl ester type epoxy resin); "EX-991L" manufactured by NagaseChemteX (epoxy resin containing alkylene oxide skeleton and butadiene skeleton); "CELLOXIDE 2021P" manufactured by Daicel (alicyclic epoxy resin with ester skeleton); "PB-3600" manufactured by Daicel; "JP-100" and "JP-200" manufactured by Nippon Soda (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemicals (liquid 1,4-glycidylcyclohexane type epoxy resin); "EG-280" manufactured by Osaka Gas Chemical (epoxy resin containing fluorene structure); "Ogsol EG-200" and "Ogsol EG-280" manufactured by Osaka Gas Chemical (epoxy resin containing Cardo structure); Nagase "EX-201" (cyclic aliphatic glycidyl ether) manufactured by ChemteX Corporation, etc.

[0240] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0241] As solid epoxy resins, preferred are biphenylol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, and phenol phthalimide-type epoxy resins.

[0242] Specific examples of solid epoxy resins include: "HP4032H" manufactured by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" and "HP-4710" manufactured by DIC Corporation (naphthalene-type tetrafunctional epoxy resin); "N-690" manufactured by DIC Corporation (cresol novolac-type epoxy resin); "N-695" manufactured by DIC Corporation (cresol novolac-type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" manufactured by DIC Corporation (dicyclopentadiene-type epoxy resin); " EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; " ESN475V", "ESN4100V" (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemicals; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemicals; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; "YX7 "700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; "WHR991S" (phenol phthalimide type epoxy resin) manufactured by Nippon Kayaku; "Ogsol PG-100" and "Ogsol CG-500" (epoxy resin containing Cardo structure) manufactured by Osaka Gas Chemical, etc.

[0243] In one embodiment, the component (B) preferably comprises an epoxy resin having an aromatic skeleton, more preferably comprises an epoxy resin having a polycyclic aromatic skeleton containing condensed rings, and further preferably comprises an epoxy resin having an aromatic skeleton, wherein the aromatic skeleton comprises one or more selected from a naphthalene skeleton and a Cardo skeleton. As the aromatic skeleton comprising a naphthalene skeleton, for example, there can be cited: a naphthol aralkyl skeleton, a naphthol novolac skeleton, a naphthalene skeleton, a naphthol skeleton, a naphthylene ether skeleton, etc., preferably a naphthol aralkyl skeleton and a naphthalene skeleton. The aromatic skeleton comprising a Cardo skeleton, including suitable examples thereof, is as described for the component (A).

[0244] The epoxy equivalent of the component (B) is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., further preferably 70 g / eq. to 1,000 g / eq., and further preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

[0245] The weight average molecular weight (Mw) of the component (B) is preferably 100 or more, more preferably 250 or more, and even more preferably 400 or more. The upper limit of the Mw of the component (B) is preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less. The weight average molecular weight (Mw) is a weight average molecular weight of a polystyrene conversion value measured by gel permeation chromatography (GPC).

[0246] In the photosensitive resin composition kit of the present invention, from the viewpoint of enjoying the effects of the present invention more and from the viewpoint of further improving the mechanical strength and insulation reliability, the content of the component (B) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, 22% by mass or more, 24% by mass or more, or 25% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, 40% by mass or less, 38% by mass or less, 36% by mass or less, or 35% by mass or less.

[0247] From the viewpoint of better enjoying the effects of the present invention, when the contents of the (A) component and the (B) component in the core resin composition are respectively set to (A) core and (B) core when the non-volatile component of the core resin composition is set to 100 mass %, (A) core and (B) core preferably satisfy the relationship of 0.1≤(A) core / (B) core≤5.

[0248] When the (A) component includes the (a1) component, the lower limit of the (A) core / (B) core ratio is more preferably greater than 0.3, further preferably greater than 0.5, further preferably greater than 0.6, greater than 0.65, greater than 0.7, greater than 0.75 or greater than 0.8, and the upper limit of the (A) core / (B) core ratio is more preferably less than 3, further preferably less than 2, further preferably less than 1.5, less than 1.4 or less than 1.2.

[0249] When the (A) component includes the (a2) component, the lower limit of the (A) core / (B) core ratio is more preferably greater than 0.3, further preferably greater than 0.5, further preferably greater than 0.7, greater than 0.9, greater than 0.95, greater than 1.0, greater than 1.05 or greater than 1.1, and the upper limit of the (A) core / (B) core ratio is more preferably less than 3, further preferably less than 2, further preferably less than 1.5, less than 1.4 or less than 1.3.

[0250] From the viewpoint of better enjoying the effects of the present invention, when the contents of the (A) component and the (B) component in the coating resin composition when the non-volatile component of the coating resin composition is set to 100 mass %, are set to (A)clad and (B)clad, respectively, (A)clad and (B)clad preferably satisfy the relationship of 0.1≤(A)clad / (B)clad≤5.

[0251] When the component (a1) is included as the component (A), the lower limit of the ratio (A) clad / (B) clad is more preferably 0.3 or more, further preferably 0.5 or more, further preferably 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, or 0.8 or more, and the upper limit of the ratio (A) clad / (B) clad is more preferably 3 or less, further preferably 2 or less, further preferably 1.5 or less, 1.4 or less, or 1.2 or less.

[0252] When the component (a2) is included as the component (A), the lower limit of the ratio (A) clad / (B) clad is more preferably 0.3 or more, further preferably 0.5 or more, further preferably 0.7 or more, 0.9 or more, 0.95 or more, 1.0 or more, 1.05 or more, or 1.1 or more, and the upper limit of the ratio (A) clad / (B) clad is more preferably 3 or less, further preferably 2 or less, further preferably 1.5 or less, 1.4 or less, or 1.3 or less.

[0253] <(C) Photocurable resin>

[0254] In the photosensitive resin composition kit of the present invention, the resin composition contains a photocurable resin as the component (C). The component (C) may be used alone or in combination of two or more.

[0255] The component (C) does not include components corresponding to the above-mentioned components (A) and (B). For example, the component (C) may not include a carboxyl group in relation to the component (a1), and may not include an epoxy group in relation to the component (a2) or the component (B).

[0256] As the component (C), for example, a (meth)acrylate compound having one or more (preferably two or more) (meth)acryloyl groups in one molecule can be used.

[0257] Examples of the (meth)acrylate compound include: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraglycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-hydroxymethylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyacrylates of polyols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or adducts of ethylene oxide, propylene oxide, or ε-caprolactone of the polyols; acrylates such as phenols such as phenyl acrylate and phenoxyethyl acrylate, or adducts of ethylene oxide or propylene oxide of the phenols; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; modified epoxy acrylates; melamine acrylates; and / or methacrylates corresponding to the above-mentioned acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferred. For example, as trivalent or higher acrylates or methacrylates, there can be mentioned trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO addition tri(meth)acrylate, glycerol PO addition tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,4-butanediol (meth)acrylate oligomers, 1,6-hexanediol (meth)acrylate oligomers, trimethylolpropane (meth)acrylate oligomers, pentaerythritol (meth)acrylate oligomers, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,N,N',N'-tetra(β-hydroxyethyl)ethyldiamine (meth)acrylate, and the like. In addition, as trivalent or higher acrylates or methacrylates, there can be mentioned: tris(2-(meth)acryloyloxyethyl)phosphate, tris(2-(meth)acryloyloxypropyl)phosphate, tris(3-(meth)acryloyloxypropyl)phosphate, tris(3-(meth)acryloyl-2-hydroxyoxypropyl)phosphate, di(3-(meth)acryloyl-2-hydroxyoxypropyl)(2-(meth)acryloyloxyethyl)phosphate, (3-(meth)acryloyl-2-hydroxyoxypropyl)di(2-(meth)acryloyloxyethyl)phosphate and other phosphate triester (meth)acrylates. Any one of these photosensitive (meth)acrylate compounds may be used alone, or two or more thereof may be used in combination. It should be noted that "EO" refers to ethylene oxide, and "PO" refers to propylene oxide.

[0258] As the component (C), commercially available products may be used, for example, "DPHA" and "TMPTA" manufactured by Nippon Kayaku Co., Ltd., and "EBECRYL 160S", "EBECRYL 895", "EBECRYL 896", "EBECRYL 3708", and "PETA" manufactured by Daicel Allnex Co., Ltd.

[0259] The weight average molecular weight (Mw) of the component (C) is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 1,000 or less, 800 or less, or 600 or less. The lower limit of the Mw of the component (C) is not particularly limited, and may be, for example, 100 or more, 150 or more, etc. The weight average molecular weight (Mw) is a weight average molecular weight of a polystyrene conversion value measured by gel permeation chromatography (GPC).

[0260] The viscosity of the component (C) is usually less than 10 Pa·s, preferably 8 Pa·s or less. The lower limit of the viscosity of the component (C) is not particularly limited, and may be, for example, 0.001 Pa·s or more, 0.005 Pa·s or more, 0.01 Pa·s or more, etc. The viscosity of the component (C) can be measured using an E-type viscometer at 25±2°C.

[0261] In the photosensitive resin composition kit of the present invention, from the viewpoint of enjoying the effects of the present invention more, the content of the component (C) in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, 44% by mass or less, 42% by mass or less, or 40% by mass or less.

[0262] From the viewpoint of being able to enjoy the effects of the present invention, when the content of the (C) component in the core resin composition when the non-volatile component of the core resin composition is set to 100% by mass is set to (C)core, and when the content of the (C) component in the coating resin composition when the non-volatile component of the coating resin composition is set to 100% by mass is set to (C)clad, (C)core and (C)clad preferably satisfy the relationship of 0.3≤(C)clad / (C)core≤3. The lower limit of the ratio of (C)clad / (C)core is more preferably 0.5 or more, more preferably 0.7 or more, and more preferably 0.9 or more or 0.95 or more, and the upper limit of the ratio of (C)clad / (C)core is more preferably 2 or less, more preferably 1.5 or less, and more preferably 1.4 or less, 1.35 or less, or 1.3 or less. In particular, if the ratio of (C)clad / (C)core is in the range of 0.9 or more and 1.5 or less, it is suitable from the viewpoint of being able to further enjoy the effects of the present invention. Therefore, in a suitable embodiment, (C)core and (C)clad satisfy the relationship of 0.9≤(C)clad / (C)core≤1.5.

[0263] From the viewpoint of better enjoying the effects of the present invention, when the contents of the (A) component and the (C) component in the core resin composition are respectively set to (A) core and (C) core when the non-volatile component of the core resin composition is set to 100 mass %, (A) core and (C) core preferably satisfy the relationship of 0.1≤(A) core / (C) core≤5.

[0264] When the (A) component includes the (a1) component, the lower limit of the (A) core / (C) core ratio is more preferably greater than 0.3, further preferably greater than 0.5, further preferably greater than 0.6, greater than 0.7, greater than 0.8, greater than 0.9 or greater than 1.0, and the upper limit of the (A) core / (C) core ratio is more preferably less than 3, further preferably less than 2, further preferably less than 1.5, less than 1.4 or less than 1.2.

[0265] When the (A) component includes the (a2) component, the lower limit of the (A) core / (C) core ratio is more preferably greater than 0.3, further preferably greater than 0.5, further preferably greater than 0.6, greater than 0.7, greater than 0.8 or greater than 0.9, and the upper limit of the (A) core / (C) core ratio is more preferably less than 3, further preferably less than 2, further preferably less than 1.5, less than 1.4 or less than 1.2.

[0266] From the viewpoint of better enjoying the effects of the present invention, when the contents of the (A) component and the (C) component in the coating resin composition when the non-volatile component of the coating resin composition is set to 100 mass %, are set to (A)clad and (C)clad, respectively, (A)clad and (C)clad preferably satisfy the relationship of 0.1≤(A)clad / (C)clad≤5.

[0267] When the component (a1) is included as the component (A), the lower limit of the ratio (A) clad / (C) clad is more preferably 0.3 or more, further preferably 0.5 or more, further preferably 0.6 or more, 0.7 or more, 0.8 or more or 0.9 or more, and the upper limit of the ratio (A) clad / (C) clad is more preferably 3 or less, further preferably 2 or less, further preferably 1.5 or less, 1.4 or less or 1.2 or less.

[0268] When the component (a2) is included as the component (A), the lower limit of the ratio (A) clad / (C) clad is more preferably 0.3 or more, further preferably 0.5 or more, further preferably 0.6 or more, 0.7 or more, 0.8 or more or 0.9 or more, and the upper limit of the ratio (A) clad / (C) clad is more preferably 3 or less, further preferably 2 or less, further preferably 1.5 or less, 1.4 or less or 1.2 or less.

[0269] <(D) Photopolymerization initiator>

[0270] In the photosensitive resin composition kit of the present invention, the resin composition contains a photopolymerization initiator as the component (D). By containing the component (D), the resin composition can be effectively photocured. The component (D) can be used alone or in combination of two or more. It should be noted that the component (D) does not contain components corresponding to the above-mentioned components (A), (B) and (C).

[0271] (D) component can use optional compounds, for example, acylphosphine oxide type photopolymerization initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; oxime ester type photopolymerization initiators such as 1,2-octanedione, 1-4-(phenylthio)-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetoxime); 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholino)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)-2-(O-benzoyl oxime); α-aminoalkylphenone (phenone) photopolymerization initiators such as [(4-(2-hydroxyethoxy)phenyl]-2-morpholinopropane-1-one); benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, etc. Sulfonium salt-based photopolymerization initiators can also be used. These can be used alone or in combination of two or more. Among these, from the viewpoint of being able to more effectively photocure the resin composition, the component (D) is preferably any of an acylphosphine oxide-based photopolymerization initiator and an oxime ester-based photopolymerization initiator, and more preferably an acylphosphine oxide-based photopolymerization initiator.

[0272] Specific examples of the component (D) include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", and "Omnirad TPO" manufactured by IGM Resins; "Irgacure OXE-01", "Irgacure OXE-02", "Irgacure TPO", and "Irgacure 819" manufactured by BASF; and "N-1919" manufactured by ADEKA.

[0273] In the photosensitive resin composition kit of the present invention, when the component (a1) is included as the component (A), from the viewpoint of being able to enjoy the effects of the present invention more, the content of the component (D) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, or 3% by mass or more, and the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, 8% by mass or less, 6% by mass or less, or 5% by mass or less.

[0274] In addition, when the component (a2) is included as the component (A), from the viewpoint of being able to better enjoy the effects of the present invention, the content of the component (D) in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, further preferably 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more, or 0.3% by mass or more, and the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less.

[0275] In the photosensitive resin composition kit of the present invention, when the component (a1) is included as the component (A), when the total amount of the non-volatile components of the components (A) and (C) of the resin composition is 100 parts by mass, the content of the component (D) in the resin composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more, and the upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, 8 parts by mass or less, or 7 parts by mass or less.

[0276] In addition, when the component (a2) is included as the component (A), when the total amount of the non-volatile components of the components (A) and (C) of the resin composition is 100 parts by mass, the content of the component (D) in the resin composition is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.3 parts by mass or more, 0.4 parts by mass or more, or 0.5 parts by mass or more, and the upper limit is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, or 1 part by mass or less.

[0277] <(E) Alkoxysilane compound>

[0278] In the photosensitive resin composition set of the present invention, at least the coating resin composition contains: an alkoxysilane compound having one or more functional groups selected from epoxy, phenylamino, vinyl and (meth)acryloyl groups as component (E). Component (E) may be used alone or in combination of two or more.

[0279] Furthermore, as long as the relationship of 0.6≤(E)clad-(E)core≤10 is satisfied, the core resin composition may contain the component (E).

[0280] The component (E) is more preferably one or more selected from the group consisting of alkoxy-containing silane coupling agents having the above-mentioned specific functional groups and oligomers thereof (hereinafter also referred to as “alkoxy oligomers”).

[0281] In one embodiment, the component (E) is an alkoxy-containing silane coupling agent represented by the following formula (E1).

[0282] X-Si(OR 1 ) a (R 2 ) 3-a (E1)

[0283] In formula (E1),

[0284] X represents a monovalent organic group having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group, and a (meth)acryloyl group,

[0285] R 1 represents an alkyl group having 1 to 3 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

[0286] R 2 represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group,

[0287] a represents an integer of 1 to 3. Here, when a is 2 or 3, a plurality of R 1 can be the same or different. In addition, when a is 1, multiple R 2 It can be the same or different.

[0288] In formula (E1), X represents a monovalent organic group having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group, and a (meth)acryloyl group.

[0289] When X represents a monovalent organic group having an epoxy group, X is preferably selected from epoxy C 6 ~C 10 Cycloalkyl-C 1 ~C 6 Alkyl, glycidyl C 6 ~C10 Aryl and glycidyloxy-C 1 ~C 6 One or more of the alkyl groups.

[0290] When X represents a monovalent organic group having a phenylamino group, X is preferably N-phenyl-amino-C 1 ~C 6 alkyl.

[0291] When X represents a monovalent organic group having a vinyl group, X is preferably selected from vinyl and vinyl-C 1 ~C 6 One or more of the alkyl groups.

[0292] When X represents a monovalent organic group having a (meth)acryloyl group, X is preferably a (meth)acryloyloxy-C 1 ~C 6 alkyl.

[0293] From the viewpoint of enjoying the effects of the present invention more, a is preferably 2 or 3, and more preferably 3.

[0294] R 2 The hydrocarbon group represented may be any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. These hydrocarbon groups are as described above, and among them, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms is preferred.

[0295] As the alkoxy-containing silane coupling agent, a commercial product can be used. As a commercial product of the alkoxy-containing silane coupling agent containing an epoxy group, there can be cited: "X-12-1231" (3-(2-glycidylphenyl)propyltrimethoxysilane), "KBM-403" (3-glycidyloxypropyltrimethoxysilane), "KBM-303" (2-(3,4)-epoxycyclohexyl)ethyltrimethoxysilane), "KBM-402" (3-glycidyloxypropylmethyldimethoxysilane), "KBE-403" (3-glycidyloxypropyltriethoxysilane), "KBE-402" (3-glycidyloxypropylmethyldiethoxysilane), "KBM-4803" (8-glycidyloxyoctyltrimethoxysilane) and the like manufactured by Shin-Etsu Chemical Co., Ltd. As commercially available products of alkoxy-containing silane coupling agents containing a phenylamino group, there can be mentioned: "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. As commercially available products of alkoxy-containing silane coupling agents containing a vinyl group, there can be mentioned: "KBE-1003" (vinyltriethoxysilane), "KBM-1003" (vinyltrimethoxysilane), "KBM-1083" (trimethoxy(7-octen-1-yl)silane) manufactured by Shin-Etsu Chemical Co., Ltd. Commercially available products of the alkoxy-containing silane coupling agent containing a (meth)acryloyl group include: "KBM-503" (3-methacryloxypropyltrimethoxysilane), "KBE-503" (3-methacryloxypropyltriethoxysilane), "KBM-502" (3-methacryloxypropylmethyldimethoxysilane), "KBE-502" (3-methacryloxypropylmethyldiethoxysilane), "KBM-5803" (8-methacryloxyoctyltrimethoxysilane), "KBM-5103" (3-acryloxypropyltrimethoxysilane), etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0296] As the alkoxy oligomer, there is no particular limitation as long as it is an oligomer of the above-mentioned alkoxy-containing silane coupling agent. Specific examples of the alkoxy oligomer include: epoxy-containing alkoxysilyl resins, phenylamino-containing alkoxysilyl resins, vinyl-containing alkoxysilyl resins, (meth)acryloyl-containing alkoxysilyl resins, etc.

[0297] Alkoxy oligomers can be commercially available. Examples of commercially available epoxy group-containing alkoxysilyl resins include "X-41-1053", "X-41-1059A", and "X-41-1056" manufactured by Shin-Etsu Chemical Co., Ltd., examples of commercially available phenylamino group-containing alkoxysilyl resins include "X-40-9281" manufactured by Shin-Etsu Chemical Co., Ltd., and examples of commercially available (meth)acryloyl group-containing alkoxysilyl resins include "X-22-164" and "X-22-164AS" manufactured by Shin-Etsu Chemical Co., Ltd.

[0298] In the photosensitive resin composition kit of the present invention, when the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is set to 100 mass % is set to (E)core, and when the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is set to 100 mass % is set to (E)clad, it is important that (E)core and (E)clad satisfy the relationship of 0.6≤(E)clad-(E)core≤10. By making (E)core and (E)clad satisfy the above relationship, the following effect of the present invention can be achieved: a single-mode optical waveguide can be manufactured with a small change in optical transmission loss before and after a reliability test. The difference between (E)core and (E)clad, i.e., the value of (E)clad-(E)core, is preferably greater than 0.8, more preferably greater than 1, further preferably greater than 1.2, greater than 1.4 or greater than 1.5, and the upper limit is preferably less than 10, more preferably less than 8, further preferably less than 6, less than 5.5, less than 5, less than 4.5 or less.

[0299] In the photosensitive resin composition set of the present invention, the content of the component (E) in the coating resin composition is 0.6% by mass or more, preferably 0.8% by mass or more, more preferably 1% by mass or more, 1.2% by mass or more, 1.4% by mass or more, or 1.5% by mass or more, and further preferably 1.6% by mass or more, 1.8% by mass or more, or 2% by mass or more, and the upper limit is preferably 14% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, or 5% by mass or less. Therefore, in one embodiment, the content of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is set to 100% by mass, i.e., (E)clad, is 1 to 12% by mass.

[0300] As described above, as long as the difference between (E) core and (E) clad, i.e., the above-mentioned relationship of (E) clad-(E) core is satisfied, the core resin composition may also include the (E) component. In the case where the core resin composition contains the (E) component, the content of the (E) component in the core resin composition is not particularly limited, preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less. The lower limit of the content may be 0% by mass, for example, it may be more than 0% by mass, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, etc.

[0301] <(F) Curing accelerator>

[0302] In the photosensitive resin composition kit of the present invention, the resin composition may contain (F) a curing accelerator as an optional component. The (F) component has a function as a curing catalyst that promotes the curing of the (B) component and the like. The (F) component may be used alone or in combination of two or more. It should be noted that the (F) component does not include components corresponding to the above-mentioned (A) to (E) components.

[0303] Examples of the component (F) include imidazole-based curing accelerators, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, the component (F) is preferably an imidazole-based curing accelerator.

[0304] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1' imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. Commercially available products of imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industries, Ltd.; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0305] Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate, and tetrabutylphosphonium bis(tetrabutylphosphonium) pyromellitic acid salt. aliphatic phosphonium salts such as tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, Aromatic phosphonium salts such as butyltriphenylphosphonium, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products reactants; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine phenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether and the like.

[0306] Examples of the urea curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1, Aromatic dimethyl urea such as 1-dimethyl urea, 3-(4-isopropylphenyl)-1,1-dimethyl urea, 3-(4-methoxyphenyl)-1,1-dimethyl urea, 3-(4-nitrophenyl)-1,1-dimethyl urea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethyl urea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethyl urea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethyl urea, N,N-(1,4-phenylene)bis(N',N'-dimethyl urea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethyl urea)[toluene bis(dimethyl urea)].

[0307] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0308] As metal curing accelerators, for example, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt acetylacetonate (II) and cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like can be cited.

[0309] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. A commercially available amine-based curing accelerator may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0310] In the photosensitive resin composition kit of the present invention, the content of the component (F) in the resin composition is not particularly limited, and may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, etc. The upper limit of the content of the component (F) in the resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less, 0.8% by mass or less, or 0.6% by mass or less.

[0311] <(G) Other additives>

[0312] In the photosensitive resin composition kit of the present invention, the resin composition may further contain (G) other additives to the extent that the purpose of the present invention is not impaired. Examples of (G) other additives include active ester curing agents, phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoic acid curing agents, Epoxy resin curing agents such as azine curing agents and cyanate curing agents; photosensitizers such as pyrazolines, anthracenes, coumarins, xanthone, and thioxanthones; inorganic fillers such as silicon dioxide, aluminum oxide, and aluminosilicates; thermoplastic resins; organic fillers, melamine, organic bentonite and other particles; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol , pyrogallol and other polymerization inhibitors; Benton, montmorillonite and other thickeners; silicone, fluorine, vinyl resin defoamers; brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters and other flame retardants; UV absorbers; plasticizers, antistatic agents, anti-aging agents, antibacterial agents, leveling agents, adhesion-imparting agents, thixotropy-imparting agents, release agents, surface treatment agents, dispersants, surface modifiers, stabilizers and other additives.

[0313] <(H) Organic solvent>

[0314] In the photosensitive resin composition kit of the present invention, the resin composition may contain an organic solvent (H) as a volatile component in combination with the non-volatile components such as the above-mentioned components (A) to (G). By containing the component (H), the viscosity of the resin composition can be adjusted, and a resin composition in the form of an ink (resin ink) can be prepared. The components (H) may be used alone or in combination of two or more.

[0315] Examples of the (H) organic solvent include ketone solvents such as methyl ethyl ketone (MEK) and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, and tetramethylbenzene; glycol ether solvents such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ester solvents such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl carbitol acetate; ether ester solvents such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl carbitol acetate, γ-butyrolactone, and methyl methoxypropionate; aliphatic hydrocarbon solvents such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0316] From the viewpoint of coating properties of the resin composition (resin ink), it is preferred to appropriately adjust the content of the component (H) in the resin composition.

[0317] [Method for producing resin composition]

[0318] In the photosensitive resin composition kit of the present invention, the resin composition can be manufactured by mixing the components to be contained in the resin composition. Therefore, in the photosensitive resin composition kit of the present invention, the core resin composition can be manufactured by mixing the components (A) to (D) and the components (E) to (H) as required, and the coating resin composition can be manufactured by mixing the components (A) to (E) and the components (F) to (H) as required. During mixing, as required, mixing can be performed using a mixing device such as a three-roller, a ball mill, a bead mill, a sand mill, etc., or stirring can be performed using a stirring device such as a super mixer, a planetary mixer, etc. There is no restriction on the mixing order of the components. In addition, cooling or heating can be performed during the mixing of the components.

[0319] [Physical properties and uses of photosensitive resin composition kit]

[0320] In the photosensitive resin composition kit of the present invention, the core resin composition can provide a cured product having a refractive index suitable for forming an optical waveguide. The refractive index of the cured product of the core resin composition is n coreThere is no particular limitation as long as an optical waveguide having a desired numerical aperture NA can be formed. For example, the refractive index n of the cured product of the core resin composition at a wavelength of 1310 nm is measured. core It is preferably 1.3 or more, more preferably 1.4 or more, and even more preferably 1.5 or more, and is preferably 2 or less, more preferably 1.9 or less, and even more preferably 1.8 or less. The refractive index n of the core resin composition is core The refractive index can be measured by the method described in <Test Example 1: Measurement of refractive index of cured product of resin composition using resin sheet> (for resin sheet) or the method described in <Test Example 8: Measurement of refractive index of cured product of resin composition using resin ink> (for resin ink) described later.

[0321] In the photosensitive resin composition kit of the present invention, the coating resin composition can provide a cured product having a refractive index suitable for forming an optical waveguide. The refractive index of the cured product of the coating resin composition is n clad There is no particular limitation as long as an optical waveguide having a desired numerical aperture NA can be formed. For example, the refractive index n of the cured product of the coating resin composition at a wavelength of 1310 nm is measured. clad It is preferably 1.3 or more, more preferably 1.4 or more, and even more preferably 1.5 or more, and is preferably 2 or less, more preferably 1.9 or less, and even more preferably 1.8 or less. The refractive index n of the coating resin composition is clad The refractive index can be measured by the method described in <Test Example 1: Measurement of refractive index of cured product of resin composition using resin sheet> (for resin sheet) or the method described in <Test Example 8: Measurement of refractive index of cured product of resin composition using resin ink> (for resin ink) described later.

[0322] The photosensitive resin composition kit of the present invention may have a refractive index n with a numerical aperture NA limited to a specific range as represented by the following formula (1): core and refractive index n clad .

[0323]

[0324] In formula (1), n core represents the refractive index of the cured product of the core resin composition, n clad Refractive index n represents the refractive index of the cured product of the coating resin composition. core and refractive index n cladThe measurement wavelength is the wavelength of light transmitted by the optical waveguide, for example, 1310 nm. Specifically, the numerical aperture NA is, for example, 0.03 or more, preferably 0.04 or more, more preferably 0.05 or more or 0.06 or more. The upper limit of the numerical aperture NA is, for example, less than 0.3, preferably 0.2 or less, more preferably 0.18 or less, and further preferably 0.16 or less or 0.15 or less.

[0325] According to the photosensitive resin composition kit of the present invention, an optical waveguide having a small value of optical transmission loss can be manufactured. For example, when the optical transmission loss of the optical waveguide is measured by the method described in <Test Example 6: Measurement of optical transmission loss> described later (for resin sheets) or the method described in <Test Example 12: Measurement of optical transmission loss> described later (for resin inks), the value of optical transmission loss (before reliability test; L1) may be preferably 0.50 dB / cm or less, more preferably 0.45 dB / cm or less, further preferably 0.44 dB / cm or less, 0.42 dB / cm or less, 0.4 dB / cm or less, or 0.38 dB / cm or less. The lower limit of the value of optical transmission loss (before reliability test; L1) is not particularly limited, and may be, for example, 0.01 dB / cm or more.

[0326] According to the photosensitive resin composition kit of the present invention, an optical waveguide having a small change in optical transmission loss before and after a reliability test can be manufactured. For example, when the optical transmission loss of the optical waveguide is measured by the method described in <Test Example 6: Measurement of Optical Transmission Loss> (for a resin sheet) described later or the method described in <Test Example 12: Measurement of Optical Transmission Loss> (for a resin ink) described later, the change rate of the optical transmission loss value (L2) after a heat and humidity resistance test (HAST test) (130°C, 85% RH, 100 hours) or a heat resistance test (reflow test) compared to the optical transmission loss value (L1) before the test can be preferably less than 40%, more preferably less than 30%, and further preferably less than 20%, less than 18%, less than 16%, less than 15%, less than 14%, less than 12%, or less than 10%. The lower limit of the change rate is not particularly limited, and may be 0% or greater. In addition to the characteristic that the value of the optical transmission loss (L1) before the test is small, the optical waveguide manufactured using the photosensitive resin composition kit of the present invention also has the characteristic that the value of the optical transmission loss (L2) after the test is small. The value of the optical transmission loss (L2) after the HAST test or the reflow test of the optical waveguide manufactured using the photosensitive resin composition kit of the present invention may be preferably 0.60 dB / cm or less, more preferably 0.55 dB / cm or less, further preferably 0.54 dB / cm or less, 0.52 dB / cm or less, 0.50 dB / cm or less, 0.48 dB / cm or less, 0.46 dB / cm or less, or 0.45 dB / cm or less. There is no particular limitation on the lower limit of the value of the optical transmission loss (L2) after the test, and for example, it may be 0.01 dB / cm or more.

[0327] The photosensitive resin composition kit of the present invention can provide excellent resolution (thin line waveguide formability) when manufacturing an optical waveguide. For example, according to the method described in <Test Example 3: Evaluation of resolution (thin line waveguide formability)> described later, when attempting to form a line layer with a thickness of 5 μm and an L / S (line / space) of 5 μm / 5 μm, a line layer with a thickness of 7 μm and an L / S (line / space) of 7 μm / 7 μm, and a line layer with a thickness of 50 μm and an L / S (line / space) of 50 μm / 50 μm, preferably, a line with a thickness of 7 μm and a line width of 7 μm or a line with a thickness of 50 μm and a line width of 50 μm can be formed, and more preferably, all of the following line layers can be formed: a line with a thickness of 5 μm and a line width of 5 μm, a line with a thickness of 7 μm and a line width of 7 μm, and a line with a thickness of 50 μm and a line width of 50 μm.

[0328] The photosensitive resin composition kit of the present invention can produce an optical waveguide having a small difference in shrinkage between the core layer and the cladding layer. For example, the shrinkage of the core layer c calculated by the method described in <Test Example 5: Evaluation of the difference in shrinkage between the core layer and the cladding layer> described later core Shrinkage rate of the coating layer c clad Difference |c core -c clad | may preferably be less than 0.07, more preferably 0.06 or less, further preferably 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less, or 0.01 or less. core -c clad The lower limit of | is not particularly limited and can be, for example, 0 or more.

[0329] According to the photosensitive resin composition kit of the present invention, an optical waveguide having good adhesion to a base layer (base substrate) can be manufactured. For example, when a resin composition layer is formed on a base circuit substrate according to the method described in <Test Example 4: Evaluation of Adhesion to Base Layer> described later and a HAST test (130°C, 85% RH, 100 hours) is performed, there is no peeling at the interface with the base circuit substrate, indicating good adhesion.

[0330] The photosensitive resin composition kit of the present invention, when used as a resin ink, can provide a cured product having a good appearance without bubbles. For example, the resin ink is applied and photocured (2 J / cm 2 When the curing is carried out by ultraviolet irradiation (190°C, 90 minutes) and heat curing (190°C, 90 minutes), a cured product with good appearance and no bubbles can be obtained.

[0331] In the photosensitive resin composition kit of the present invention, the core resin composition can be used as a resin composition for forming a core layer of an optical waveguide. For example, the core resin composition can be used to form an optical waveguide that can transmit light with a wavelength of 1300nm to 1320nm. In particular, the core resin composition is preferably used to form a single-mode optical waveguide, for example, preferably used to form an optical waveguide that is single-mode for light with a wavelength of 1310nm.

[0332] In the photosensitive resin composition kit of the present invention, the coating resin composition can be used as a resin composition for forming a coating layer of an optical waveguide. For example, the coating resin composition can be used to form an optical waveguide that can transmit light with a wavelength of 1300nm to 1320nm. In particular, the coating resin composition is preferably used to form a single-mode optical waveguide, for example, preferably used to form an optical waveguide that is single-mode for light with a wavelength of 1310nm.

[0333] Thus, the photosensitive resin composition kit of the present invention can be suitably used for manufacturing an optical waveguide, and more suitably used for manufacturing an optical waveguide capable of transmitting light having a wavelength of 1300 nm to 1320 nm. In addition, the photosensitive resin composition kit of the present invention is particularly suitably used for manufacturing a single-mode optical waveguide.

[0334] [Photosensitive resin sheet set]

[0335] The resin compositions in the photosensitive resin composition set of the present invention can be used to produce a resin sheet. Specifically, the core resin composition can be used to produce a core resin sheet, and the coating resin composition can be used to produce a coating resin sheet. The present invention also provides a photosensitive resin sheet set comprising the core resin sheet and the coating resin sheet.

[0336] In the photosensitive resin sheet set of the present invention, the core resin sheet comprises a resin composition layer comprising the core resin composition in the photosensitive resin composition set of the present invention, and the covering resin sheet comprises a resin composition layer comprising the covering resin composition in the photosensitive resin composition set of the present invention.

[0337] The photosensitive resin sheet set of the present invention can be suitably used for producing an optical waveguide. According to the photosensitive resin sheet set of the present invention, the same advantages as the above-mentioned photosensitive resin composition set can be obtained, and further, since the optical waveguide can be produced by lamination, the optical waveguide can be produced more simply.

[0338] In one embodiment, the photosensitive resin sheet set of the present invention comprises:

[0339] A core resin sheet comprising a support and a resin composition layer containing a core resin composition provided on the support; and

[0340] A coating resin sheet comprises a support and a resin composition layer provided on the support and containing a coating resin composition.

[0341] Examples of the support include polyethylene terephthalate films, polyethylene naphthalate films, polypropylene films, polyethylene films, polyvinyl alcohol films, triacetoacetate films, and the like. Polyethylene terephthalate films are particularly preferred.

[0342] As commercially available supports, for example, there can be cited: products named "ALPHAN MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd.; polypropylene films manufactured by Shin-Etsu Film Co., Ltd.; polyethylene terephthalate films of PS series such as "PS-25" manufactured by Teijin Co., Ltd., etc., but are not limited to these. For these supports, in order to easily remove the resin composition layer, a release agent such as a silicone coating agent can be applied to the surface. The thickness of the support is preferably in the range of 5μm to 50μm, and more preferably in the range of 10μm to 25μm. By setting the thickness to 5μm or more, the support can be prevented from breaking when the support is peeled off before development, and by setting the thickness to 50μm or less, the resolution when exposed from the support can be improved. In addition, a support with low fisheye is preferred. Here, fisheye refers to a substance formed by mixing foreign matter, unmelted matter, oxidative degradation products, etc. of the material into the film when the film is manufactured by mixing, extrusion, biaxial stretching, casting, etc. after the material is hot-melted.

[0343] Furthermore, in order to reduce light scattering caused by active light such as ultraviolet rays during exposure, the support preferably has excellent transparency. Specifically, the support preferably has a turbidity (haze standardized according to JIS-K6714) of 0.1 to 5 as an index of transparency.

[0344] In the photosensitive resin sheet set of the present invention, whether it is a core resin sheet or a coating resin sheet, the resin composition layer can be protected by a protective film. By protecting the resin composition layer side of the resin sheet with a protective film (covering film), dust and the like can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer. As a protective film, a film composed of the same material as the above-mentioned support can be used. There is no particular limitation on the thickness of the protective film, preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and further preferably in the range of 10 μm to 30 μm. By setting the thickness to more than 1 μm, the operability of the protective film can be improved, and by setting it to less than 40 μm, it tends to be cheaper. It should be noted that the adhesion between the resin composition layer and the protective film of the protective film is preferably smaller than the adhesion between the resin composition layer and the support.

[0345] The resin sheet can be manufactured, for example, by the following method: modulating a resin varnish obtained by dissolving the resin composition of the present invention in an organic solvent, applying the resin varnish on a support, and drying the organic solvent by heating or blowing hot air, etc. to form a resin composition layer. In the case of manufacturing a core resin sheet, a core resin composition can be used, and in the case of manufacturing a coating resin sheet, a coating resin composition can be used. Specifically, first, after removing the bubbles in the resin composition by a vacuum degassing method, the resin composition is applied to a support, the solvent is removed by a hot air furnace or a far infrared furnace, and it is dried, and then a protective film is laminated on the obtained resin composition layer as needed, thereby manufacturing a resin sheet. The specific drying conditions vary depending on the curability of the resin composition or the amount of organic solvent in the resin varnish. For a resin varnish containing 30% to 60% by mass of an organic solvent, it can be dried at 80°C to 120°C for 3 minutes to 13 minutes. From the perspective of preventing the diffusion of the organic solvent in the subsequent process, the amount of the residual organic solvent in the resin composition layer is preferably set to 5% by mass or less, and more preferably set to 2% by mass or less relative to the total amount of the resin composition layer. Those skilled in the art can appropriately set suitable drying conditions through simple experiments.

[0346] In the photosensitive resin sheet set of the present invention, the thickness of the resin composition layer of the core resin sheet is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 3 μm or more, and is preferably 100 μm or less, more preferably 50 μm or less, further preferably 20 μm or less.

[0347] In the photosensitive resin sheet set of the present invention, the thickness of the resin composition layer of the coating resin sheet is preferably 5 μm or more, more preferably 7 μm or more, further preferably 10 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, further preferably 30 μm or less or 20 μm or less.

[0348] Examples of coating methods for the resin composition include gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, cavity gravure coating, slot coating, spray coating, and dip coating.

[0349] The resin composition can be applied several times, or once, or a combination of different methods. The coating method of the resin composition is preferably a die coating method with excellent uniform coating properties. In addition, in order to avoid foreign matter from mixing in, the coating process is preferably carried out in an environment where foreign matter is less generated, such as a clean room.

[0350] [Photosensitive resin ink set]

[0351] As described above, the photosensitive resin composition kit of the present invention can be used as resin ink (resin varnish). The present invention also provides the resin ink kit.

[0352] The photosensitive resin ink set of the present invention comprises a core resin ink and a coating resin ink. Here, the core resin ink can be prepared by adding an organic solvent to the core resin composition as required, and the coating resin ink can be prepared by adding an organic solvent to the coating resin composition as required. Hereinafter, the core resin ink and the coating resin ink may be collectively referred to as "resin ink".

[0353] In the photosensitive resin ink set of the present invention, the content of the organic solvent in the resin ink is preferably adjusted so that the residual organic solvent content measured by the method described in <Test Example 10: Analysis of organic solvent in resin composition layer by GC / MS (gas chromatography mass spectrometry)> described later is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less or 2.5% by mass or less. By containing the organic solvent so that the residual organic solvent content is less than the above-mentioned upper limit, an optical waveguide with a smaller change in optical transmission loss before and after the reliability test can be manufactured. There is no particular limitation on the lower limit of the residual organic solvent content, and it may be 0% by mass or more than 0% by mass.

[0354] [Optical waveguide]

[0355] The optical waveguide can be manufactured by using any of the above-mentioned photosensitive resin composition set, photosensitive resin sheet set and photosensitive resin ink set. The present invention also provides the above-mentioned optical waveguide. The embodiments of the optical waveguide are described below using the accompanying drawings.

[0356] Figure 1 FIG. 1 is a perspective view schematically showing an optical waveguide 10 according to an embodiment of the present invention. Figure 1 As shown, the optical waveguide 10 comprises a core layer 100 and a cladding layer 200. The core layer 100 comprises a cured product of the core resin composition of the photosensitive resin composition set of the present invention, and preferably comprises only a cured product of the core resin composition of the photosensitive resin composition set of the present invention. In addition, the cladding layer 200 comprises a cured product of the coating resin composition of the photosensitive resin composition set of the present invention, and preferably comprises only a cured product of the coating resin composition of the photosensitive resin composition set of the present invention.

[0357] The core layer 100 is disposed in the cladding layer 200. Therefore, the core layer 100 is covered by the cladding layer 200. Typically, the entire circumference of the core layer 100 is covered by the cladding layer 200. The core layer 100 and the cladding layer 200 are in direct contact without passing through other layers, and therefore, an interface 100I may be formed between the core layer 100 and the cladding layer 200. Typically, the core layer 100 has a higher refractive index than the cladding layer 200, and therefore, light (not shown) may be transmitted within the core layer 100 from one end (end on the incident side) 100A of the core layer 100 to the other end (end on the exit side) 100B.

[0358] The wavelength of light that can be transmitted by the optical waveguide 10 can be selected in various ways. For example, the preferred wavelength range of the transmitted light can be 840nm to 860nm (e.g., 850nm), 1300nm to 1320nm (e.g., 1310nm), 1540nm to 1560nm (e.g., 1550nm), etc. Among them, the wavelength range of the light transmitted by the optical waveguide 10 is preferably 1300nm to 1320nm.

[0359] The optical waveguide 10 may be a single-mode optical waveguide or a multi-mode optical waveguide, but is preferably a single-mode optical waveguide. The optical waveguide 10 is preferably a single-mode optical waveguide for light in the preferred wavelength range. For example, the optical waveguide 10 is preferably a single-mode optical waveguide for light of 1310 nm.

[0360] The width L of the core layer 100 is preferably set appropriately within the range in which light can be transmitted. The specific range of the line width L of the core layer 100 is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 2 μm or more, preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less, 10 μm or less, or 5 μm or less. The width L of the core layer 100 is equivalent to the line width (line) of the core layer 100 when observed from the thickness direction.

[0361] The spacing S of the core layer 100 is preferably set appropriately within a range that allows light transmission. The specific range of the spacing S of the core layer 100 is preferably 50 μm or more, more preferably 70 μm or more, and further preferably 100 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less, and further preferably 300 μm or less. The spacing S of the core layer 100 is equivalent to the spacing (space) of the core layer observed from the thickness direction.

[0362] The thickness T of the core layer 100 is preferably set appropriately within a range that allows light transmission. Specifically, the thickness T of the core layer 100 is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 2 μm or more, and preferably 50 μm or less, more preferably 30 μm or less, and further preferably 20 μm or less or 10 μm or less.

[0363] The thickness of the cladding layer 200 is usually greater than that of the core layer 100. The specific thickness of the cladding layer 200 is preferably 5 μm or more, more preferably 7 μm or more, and further preferably 10 μm or more, and preferably 100 μm or less, more preferably 60 μm or less, and further preferably 40 μm or less or 30 μm or less.

[0364] If necessary, the optical waveguide 10 may include optional components other than the core layer 100 and the cladding layer 200. For example, the optical waveguide 10 may include a conductor layer (not shown) formed by plating or the like on the core layer, and a substrate 300. In the optical waveguide 10 including the substrate 300, the cladding layer 200 is usually provided on the substrate 300, and the core layer 100 is provided in the cladding layer 200.

[0365] As the substrate 300, a hard substrate such as a glass substrate, a metal substrate, a ceramic substrate, a wafer, and a circuit substrate can be used. As a wafer, for example, a semiconductor wafer such as a silicon wafer, a gallium arsenide (GaAs) wafer, an indium phosphide (InP) wafer, a gallium phosphide (GaP) wafer, a gallium nitride (GaN) wafer, a gallium telluride (GaTe) wafer, a zinc selenide (ZnSe) wafer, and a silicon carbide (SiC) wafer can be used, and a dummy wafer can also be used. As a dummy wafer, for example, a plate-shaped member having a molded resin and an electronic component buried in the molded resin can be used. As a circuit substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. can be cited. It should be noted that, here, the circuit substrate refers to a substrate having a conductor layer (circuit) processed by patterning formed on one side or both sides of the above-mentioned substrate. In addition, as the substrate 300, a film formed of a plastic material such as polyethylene terephthalate, polyimide, and polyester can be used. Also, a flexible circuit substrate may be employed as the substrate 300 .

[0366] In addition, the optical waveguide 10 may include a protective layer (not shown) for protecting the core layer 100 and the cladding layer 200 as an optional component. The protective layer may be provided, for example, to cover the surface of the cladding layer 200 opposite to the substrate 300 .

[0367] [Method for manufacturing optical waveguide]

[0368] The optical waveguide 10 can be produced using the photosensitive resin composition kit of the present invention.

[0369] Hereinafter, an embodiment including component (a1) as component (A) (hereinafter also referred to as “first embodiment”; core formation based on alkali development) and an embodiment including component (a2) as component (A) (hereinafter also referred to as “second embodiment”; core formation based on etching) are described.

[0370] -First Embodiment (Formation of Core Layer by Alkali Development)-

[0371] In one embodiment, the resin composition in the photosensitive resin composition kit of the present invention contains a carboxyl group-containing resin (a1) as component (A). The resin composition containing the component (a1) is soluble in an alkaline developer and can be alkali developed. Hereinafter, an embodiment in which a core layer is formed by alkali development, that is, the first embodiment, is described.

[0372] In the first embodiment, the optical waveguide 10 can be manufactured by a method including the following steps in sequence:

[0373] A step (I) of forming a first composition layer comprising a coating resin composition;

[0374] Step (II) of curing the first composition layer;

[0375] A step (III) of forming a second composition layer including a core resin composition on the first composition layer;

[0376] A step (IV) of subjecting the second composition layer to an exposure treatment;

[0377] A step (V) of subjecting the second composition layer to a development treatment;

[0378] A step (VI) of curing the second composition layer;

[0379] a step (VII) of forming a third composition layer comprising a coating resin composition on the second composition layer; and

[0380] A step (VIII) of curing the third composition layer.

[0381] Furthermore, if necessary, after the step (VIII) is completed, the step (IX) of forming a conductor layer on the coating layer may be included.

[0382] Figure 2 1 is a schematic cross-sectional view for explaining step (I) of the method for manufacturing the optical waveguide according to the first embodiment. Figure 2 As shown, the method for producing an optical waveguide according to the first embodiment includes a step (I) of forming a first composition layer 210 containing a coating resin composition. In this embodiment, an example of forming the first composition layer 210 on a substrate 300 is shown and described.

[0383] There is no particular limitation on the method for forming the first composition layer 210. For example, the first composition layer 210 can be formed by coating the coating resin composition on the substrate 300. From the viewpoint of smooth coating, a varnish-like coating resin composition containing a solvent may be prepared and then coated.

[0384] As coating methods, for example, there can be mentioned: gravure coating method, micro gravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, cavity gravure coating method, slot method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, rod coating method, glue coater method, air knife coating method, curtain flow coating method, offset printing method, brush coating method, screen printing method, etc.

[0385] The coating resin composition can be applied once or multiple times. In addition, different coating methods can be combined. In order to avoid the mixing of foreign matter, the coating is preferably carried out in an environment where there is little foreign matter such as a clean room.

[0386] After the coating of the coating resin composition, the first composition layer 210 can be dried as needed. Drying can be carried out by a drying device such as a hot air furnace, a far infrared furnace, etc. The drying conditions are preferably set appropriately according to the composition of the coating resin composition. For example, the drying temperature is preferably above 50°C, more preferably above 70°C, and further preferably above 80°C, preferably below 150°C, more preferably below 130°C, and further preferably below 120°C. In addition, the drying time is preferably above 30 seconds, more preferably above 60 seconds, and further preferably above 120 seconds, preferably below 60 minutes, more preferably below 20 minutes, and further preferably below 5 minutes.

[0387] The first composition layer 210 can be formed by, for example, using a coating resin sheet. For example, by laminating the resin composition layer of the coating resin sheet on the substrate 300, the first composition layer 210 can be formed on the substrate 300. Lamination is usually performed by pressing the resin composition layer of the coating resin sheet on the substrate 300 while heating it. The lamination is preferably performed under reduced pressure by a vacuum lamination method. In addition, before lamination, a preheating treatment of heating the resin sheet and the substrate can be performed as needed.

[0388] The lamination conditions may be, for example, a lamination temperature of 70°C to 140°C and a lamination pressure of 1 kgf / cm 2 ~11kgf / cm 2 (9.8×10 4 N / m2 ~107.9×10 4 N / m 2 ) and the pressing time is 5 seconds to 300 seconds. In addition, lamination is preferably carried out under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. Lamination can be carried out intermittently or continuously using a roller.

[0389] The vacuum lamination method can be performed using a commercially available vacuum laminator, such as a vacuum applicator manufactured by Nikko-Materials, a vacuum pressure laminator manufactured by Meiki Manufacturing, a roll dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC.

[0390] When the first composition layer 210 is formed using a coating resin sheet having a support, the support is usually peeled off at an appropriate time before step (III).

[0391] In step (I), the first composition layer 210 formed on the substrate 300 usually contains a coating resin composition, and preferably contains only a coating resin composition.

[0392] The method for producing an optical waveguide according to the first embodiment includes, after step (I), step (II) of curing the first composition layer 210. Step (II) can be performed, for example, by heat treating the first composition layer 210. The conditions for the heat treatment can be selected according to the type and amount of the resin component in the coating resin composition, and are preferably in the range of 150° C. to 250° C. for 20 minutes to 180 minutes, and more preferably in the range of 160° C. to 230° C. for 30 minutes to 120 minutes. The heat treatment is preferably performed in an inert atmosphere such as a nitrogen atmosphere.

[0393] In addition, the curing of the first composition layer 210 can be performed by exposure treatment. In one example, the specific exposure dose range is preferably 10 mJ / cm 2 More preferably, 50 mJ / cm 2 More preferably, 200 mJ / cm 2 More than, preferably 10,000 mJ / cm 2 Less than, more preferably 8,000 mJ / cm 2 Below, more preferably 4,000 mJ / cm 2 Below, 3,000mJ / cm 2 Below, 2,000mJ / cm 2 Below or 1,000mJ / cm 2Alternatively, the first composition layer 210 may be cured by combining exposure treatment and heat treatment.

[0394] When the first composition layer 210 is formed using a coating resin sheet having a support, in step (II), a support (not shown) may be present on the first composition layer 210. When a support is present on the first composition layer 210, exposure may be performed through the support or after peeling off the support.

[0395] Figure 3 1 is a schematic cross-sectional view for explaining step (II) of the method for manufacturing the optical waveguide according to the first embodiment. Figure 3 As shown, by curing the first composition layer 210 in step (II), a first composition layer 220 cured on the substrate 300 is obtained. The cured first composition layer 220 forms a part of the coating layer 200, and is sometimes referred to as a "lower coating layer" 220 below.

[0396] Figure 4 1 is a schematic cross-sectional view for explaining step (III) of the method for manufacturing the optical waveguide according to the first embodiment. Figure 4 As shown, the method for producing an optical waveguide according to the first embodiment includes, after step (II), step (III) of forming a second composition layer 110 including a core resin composition on the lower cladding layer 220 which is the cured first composition layer.

[0397] There is no particular limitation on the method for forming the second composition layer 110. For example, the second composition layer 110 can be formed by coating the core resin composition on the lower coating layer 220. From the viewpoint of smooth coating, a varnish-like core resin composition containing a solvent can be prepared, and then the varnish-like core resin composition can be coated. The coating of the core resin composition can be carried out in the same manner as the coating of the coating resin composition. In addition, after the coating of the core resin composition, the second composition layer 110 can be dried as needed. The drying of the second composition layer 110 can be carried out by the same method and conditions as the drying of the first composition layer 210.

[0398] The second composition layer 110 can be formed, for example, using a core resin sheet. For example, by laminating the resin composition layer of the core resin sheet on the lower coating layer 220, the second composition layer 110 can be formed on the lower coating layer 220. The lamination of the core resin sheet can be performed in the same manner as the lamination of the coating resin sheet. In addition, the support of the core resin sheet is peeled off at an appropriate time before step (V).

[0399] In step (III), the second composition layer 110 formed on the lower cladding layer 220 includes the core resin composition, and preferably includes only the core resin composition.

[0400] Figure 5 1 is a schematic cross-sectional view for explaining step (IV) of the method for manufacturing the optical waveguide according to the first embodiment. Figure 5 As shown, the method for producing the optical waveguide according to the first embodiment includes, after the step (III), the step (IV) of subjecting the second composition layer 110 to an exposure treatment.

[0401] In step (IV), a latent image is formed on the second composition layer 110 by exposure treatment. Specifically, in the exposure treatment, light P is selectively irradiated to a specific portion of the second composition layer 110. Therefore, when the exposure treatment is performed, an exposure portion 111 irradiated with light and a non-exposed portion 112 not irradiated with light are provided on the second composition layer 110. Generally, since the core resin composition functions as a negative photosensitive resin composition, a latent image corresponding to the core layer is formed by the exposure portion 111.

[0402] From the viewpoint of selective exposure, the exposure treatment in step (IV) is usually performed using a mask 400. Specifically, in the exposure treatment, light P is irradiated to the second composition layer 110 via a mask 400 having a light-transmitting portion 410 and a light-shielding portion 420. The light P passes through the light-transmitting portion 410 and enters the exposure portion 111, but cannot pass through the light-shielding portion 420 and cannot enter the non-exposure portion 112. Therefore, the exposure portion 111 and the non-exposure portion 112 corresponding to the light-transmitting portion 410 and the light-shielding portion 420 may be provided on the second composition layer 110. Figure 5 As shown, the mask 400 may be in close contact with the second composition layer 110 (contact exposure method), or may be not in close contact and exposure may be performed using parallel light (non-contact exposure method).

[0403] Generally, the light-transmitting portion 410 of the mask 400 is formed to have a planar shape corresponding to the core layer of the optical waveguide. Therefore, the light-shielding portion 420 of the mask 400 is formed to have a planar shape corresponding to the portion of the optical waveguide without the core layer. Unless otherwise specified, the "planar shape" means the shape observed from the thickness direction. Hereinafter, the light-transmitting portion 410 formed in a planar shape corresponding to the core layer is sometimes referred to as a "mask pattern".

[0404] As the light P used in the exposure treatment in step (IV), the same range of active light as that of the exposure treatment of the first composition layer 210 in step (II) can be used. The exposure amount of the light P is preferably set so that the desired core layer can be formed after curing in step (VII). In one example, the specific range of the exposure amount in step (IV) can be the same range as that of the exposure amount of the first composition layer 210 in step (II).

[0405] When the second composition layer 110 is formed using a core resin sheet having a support, in step (IV), a support (not shown) may be present on the second composition layer 110. When a support is present on the second composition layer 110, exposure may be performed through the support or after peeling off the support.

[0406] Since the core resin composition functions as a negative photosensitive resin composition, the solubility in the developer is reduced in the exposed portion 111. On the other hand, the solubility in the developer is high in the non-exposed portion 112. The difference in solubility between the exposed portion 111 and the non-exposed portion 112 is utilized to perform the development treatment in the subsequent step (VI).

[0407] From the viewpoint of curing the second composition layer 110, the method for producing an optical waveguide according to the first embodiment may include a step (X) of heating the second composition layer 110 after the step (IV) and before the step (V). The step (X) can rapidly reduce the solubility of the exposed portion 111 in the developer. The heating in the step (X) may be performed on a hot plate or in an oven. The heating temperature may be, for example, 40° C. to 110° C. In addition, the heating time may be, for example, 30 seconds to 60 minutes.

[0408] Figure 6 1 is a schematic cross-sectional view for explaining step (V) of the method for manufacturing an optical waveguide according to the first embodiment. The method for manufacturing an optical waveguide according to the first embodiment includes, after step (IV), a step (V) of performing a development treatment on the second composition layer 110. The latent image formed in step (IV) can be developed by the development treatment. Figure 6 As shown, since the core resin composition functions as a negative photosensitive resin composition, the exposure portion 111 is not removed by the development process, but the non-exposure portion 112 is removed (see Figure 5 The exposed portion 111 of the second composition layer 110 remaining after development may have the same light-transmitting portion 410 as the light-transmitting portion 410 of the mask 400 used in step (IV) (see Figure 5 ) has the same planar shape as the mask pattern.

[0409] The developing method is generally a wet developing method in which the second composition layer 110 is brought into contact with a developer. As the developer, an alkaline aqueous solution is generally used.

[0410] As for the alkaline aqueous solution as a developer, for example, there can be mentioned: an aqueous solution of an alkali metal compound. As the alkali metal compound, for example, there can be mentioned: an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide; an alkali metal carbonate or bicarbonate such as sodium carbonate, sodium bicarbonate; an alkali metal carbonate such as sodium phosphate, potassium phosphate; an alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate, etc. In addition, as the alkaline aqueous solution, for example, there can be mentioned: an aqueous solution of an organic base that does not contain metal ions such as tetramethylammonium hydroxide. The alkaline aqueous solution may be used alone or in combination of two or more. Among them, from the viewpoint of significantly obtaining the effect of the present invention, the alkaline aqueous solution is preferably an aqueous solution of an organic base that does not contain metal ions.

[0411] If necessary, the developer may contain additives such as a surfactant and a defoaming agent in order to improve the developing effect.

[0412] The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 20° C. or higher, preferably 50° C. or lower, and more preferably 40° C. or lower.

[0413] Examples of developing methods include a paddle method, a spray method, an immersion method, a brushing method, a slapping method, and an ultrasonic method. Among them, the spray method is suitable for improving resolution. When the spray method is used, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0414] After development using a developer, the second composition layer 110 may be rinsed. The rinsing is preferably performed using a solvent different from the developer. For example, the same type of solvent as that contained in the core resin composition or water may be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

[0415] After development using a developer, desmear treatment may be performed to remove non-exposed areas that cannot be removed by development. The desmear treatment may be performed by various methods known to those skilled in the art used in the production of printed wiring boards.

[0416] The method for producing an optical waveguide according to the first embodiment includes, after step (V), step (VI) of curing the second composition layer 110. The step (VI) generally includes heat-treating the second composition layer 110. The conditions for the heat treatment can be selected according to the type and amount of the resin component in each resin composition in the photosensitive resin composition kit of the present invention. For example, the conditions for the heat treatment in step (VI) may be the same as those for the heat treatment of the first composition layer 210 in step (II).

[0417] Figure 7 1 is a schematic cross-sectional view for explaining step (VI) of the method for manufacturing the optical waveguide according to the first embodiment. Figure 7 As shown, by curing the second composition layer 110 in step (VI), the core layer 100 as the cured second composition layer is obtained on the lower cladding layer 220 .

[0418] Figure 8 1 is a schematic cross-sectional view for explaining step (VII) of the method for manufacturing the optical waveguide according to the first embodiment. Figure 8 As shown, the method for manufacturing an optical waveguide according to the first embodiment includes, after step (VI), step (VII) of forming a third composition layer 230 including a cladding resin composition on the core layer 100. The third composition layer 230 is generally formed to cover the entire surface of the peripheral surface of the core layer 100 that is not in contact with the lower cladding layer 220. Therefore, the third composition layer 230 is formed to cover the core layer 100 and also formed on the lower cladding layer 220.

[0419] There is no particular limitation on the method for forming the third composition layer 230. For example, the third composition layer 230 can be formed by applying a coating resin composition on the core layer 100 (and on the lower coating layer 220 as required). The coating of the coating resin composition for forming the third composition layer 230 can be performed in the same manner as the coating of the coating resin composition for forming the first composition layer 210. In addition, after the coating of the coating resin composition, the third composition layer 230 can be dried as required. The drying of the third composition layer 230 can be performed by the same method and conditions as the drying of the first composition layer 210.

[0420] The third composition layer 230 can be formed by using a coating resin sheet, for example. For example, by laminating a resin composition layer of a coating resin sheet on the core layer 100 (and the lower coating layer 220 as required), the third composition layer 230 can be formed on the core layer 100. The lamination of the coating resin sheet for forming the third composition layer 230 can be performed in the same manner as the lamination of the coating resin sheet for forming the first composition layer 210. When the third composition layer 230 is formed using a coating resin sheet having a support, the support can be peeled off in any process.

[0421] In step (VII), the third composition layer 230 formed on the core layer 100 includes a coating resin composition, and preferably includes only a coating resin composition.

[0422] The method for producing an optical waveguide according to the first embodiment includes, after step (VII), step (VIII) of curing the third composition layer 230. The curing of the third resin composition layer 230 in step (VIII) can be generally performed in the same manner as the curing of the first composition layer 210.

[0423] Fig. 9 1 is a schematic cross-sectional view for explaining step (VIII) of the method for manufacturing the optical waveguide according to the first embodiment. Fig. 9 As shown, by curing the third composition layer 230 in step (VIII), a third composition layer 240 cured on the core layer 100 is obtained. The cured third composition layer 240 forms a part of the cladding layer 200, and is sometimes referred to as the "upper cladding layer" 240 below. Then, the cladding layer 200 is formed by the upper cladding layer 240 and the lower cladding layer 220. Therefore, the optical waveguide 10 having the cladding layer 200 including the lower cladding layer 220 and the upper cladding layer 240, and the core layer 100 provided on the cladding layer 200 can be obtained.

[0424] Fig.10 It is a schematic cross-sectional view for explaining the step (IX) of the method for manufacturing an optical waveguide involved in one embodiment of the present invention. The method for manufacturing an optical waveguide involved in one embodiment of the present invention may include a step (IX) of forming a conductor layer on the cladding layer after the step (VIII) is completed. The conductor layer 500 formed on the upper cladding layer 240 is preferably formed by electroplating. In addition, before forming the conductor layer 500 by electroplating, the surface of the upper cladding layer 240 may be roughened. Since the upper cladding layer 240 contains the photosensitive resin composition of the present invention, even if the arithmetic mean roughness (Ra) after the roughening treatment is small, the peel strength between the core layer 100 and the conductor layer 500 can be improved.

[0425] The steps and conditions of the roughening treatment are not particularly limited. For example, the insulating layer may be roughened by sequentially performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution.

[0426] As the swelling liquid used for the roughening treatment, for example, there can be mentioned: an alkaline solution, a surfactant solution, etc., preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. As commercially available swelling liquids, for example, there can be mentioned: "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU" manufactured by Atotech Japan, etc. There are no particular limitations on the swelling treatment based on the swelling liquid, and for example, it can be carried out by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0427] As an oxidant for roughening treatment, for example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment based on an oxidant such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As a commercially available oxidant, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan can be cited.

[0428] As the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferred, and commercially available products include, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidant in the neutralizing solution at 30°C to 80°C for 5 to 30 minutes. In view of operability, etc., it is preferred to immerse the object subjected to the roughening treatment with the oxidant in the neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0429] The arithmetic mean roughness Ra of the surface of the upper coating layer after the roughening treatment is preferably 500 nm or less, more preferably less than 400 nm, further preferably 200 nm or less, and more preferably less than 200 nm. The lower limit is not particularly limited, and can be, for example, 1 nm or more, 2 nm or more, etc.

[0430] After the roughening treatment is completed, the conductor layer 500 is formed on the upper cladding layer 240 subjected to the roughening treatment. Specifically, the surface of the core layer 100 can be electroplated by a semi-additive method, a full-additive method, or the like to form the conductor layer 500 having a desired wiring pattern. From the perspective of simplicity of manufacturing, it is preferred to form the conductor layer by a semi-additive method. The following is an example of forming a conductor layer by a semi-additive method.

[0431] On the surface of the upper cladding layer 240, a plating seed layer is formed by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer 500 having a desired wiring pattern can be formed.

[0432] The method for producing the optical waveguide 10 may further include an optional step in combination with the above-mentioned steps.

[0433] The method for manufacturing the optical waveguide 10 may include, for example, a step of forming a protective layer (not shown). In addition, the method for manufacturing the optical waveguide 10 may include, for example, a step of cutting the manufactured optical waveguide 10 .

[0434] The method for manufacturing the optical waveguide 10 may repeat the above steps. For example, steps (I) to (IX) may be repeated to manufacture an optical waveguide having a multilayer structure in which core layers and cladding layers are alternately provided in the thickness direction on the substrate 300 .

[0435] - Second Embodiment (Formation of Core Layer by Etching) -

[0436] In one embodiment, the resin composition in the photosensitive resin composition kit of the present invention contains a resin (a2) containing an epoxy group and a free radical polymerizable group as component (A). The resin composition containing component (a2) can be patterned by etching. Hereinafter, an embodiment in which a core layer is formed by patterning based on etching, i.e., a second embodiment, will be described.

[0437] In the second embodiment, the optical waveguide 10 can be manufactured by a method including the following steps in sequence:

[0438] A step (i) of forming a first composition layer comprising a coating resin composition;

[0439] (ii) curing the first composition layer;

[0440] (iii) forming a second composition layer including a core resin composition on the first composition layer;

[0441] (iv) a step of curing the second composition layer;

[0442] (v) forming a fourth composition layer comprising a resist composition on the second composition layer;

[0443] (vi) subjecting the fourth composition layer to an exposure treatment;

[0444] (vii) subjecting the fourth composition layer to a development treatment;

[0445] (viii) forming a pattern on the second composition layer;

[0446] A step (x) of forming a third composition layer comprising a coating resin composition on the second composition layer; and

[0447] The step (xi) of curing the third composition layer.

[0448] In addition, if necessary, after step (viii) and before step (x), a step (ix) of removing the fourth composition layer may be included. In addition, if necessary, after step (xi) is completed, a step (xii) of forming a conductor layer on the coating layer may be included.

[0449] In the second embodiment, step (i), step (ii) and step (iii) can be carried out in the same manner as step (I), step (II) and step (III) in the first embodiment, respectively.

[0450] In the method for producing an optical waveguide according to the second embodiment, in steps (iv) to (viii), the cured product of the core resin composition is etched through a photoresist (resist) to form a pattern.

[0451] In step (iv), the second composition layer is cured. Step (iv) may be performed by heat treatment or exposure treatment. The conditions of the heat treatment and exposure treatment may be selected according to the type and amount of the resin component in the core resin composition. For example, the conditions of the heat treatment and exposure treatment in step (iv) may be the same as those of the heat treatment and exposure treatment in step (II).

[0452] In step (v), a fourth composition layer comprising a resist composition is formed on the second composition layer. As the resist composition, a composition comprising a resin that can be developed in a developer such as an alkaline aqueous solution is preferably used. As the resist composition, a material known in the art for use as a photoresist can be used, for example, an acrylic resin, etc.

[0453] In the process (v), there is no particular restriction on the formation method of the fourth composition layer. For example, by applying the resist composition on the second composition layer, the fourth composition layer can be formed. The coating of the fourth composition layer can be carried out in the same manner as the coating of the coating resin composition for forming the first composition layer in the process (I). In addition, after the coating of the resist composition, the fourth composition layer can be dried as required. The drying of the fourth composition layer can adopt the same method and conditions as the drying of the first composition layer. In addition, the fourth composition layer can be formed by stacking a dry film containing the resist composition. The stacking conditions of the dry film are preferably appropriately set according to the physical properties of the dry film.

[0454] In step (vi), the fourth composition layer is subjected to exposure treatment, and then, in step (vii), the fourth composition layer is subjected to development treatment. These steps (vi) and (vii) can be appropriately implemented according to the composition of the resist composition used. For example, steps (vi) and (vii) can be implemented in the same manner as steps (IV) and (V) in the first embodiment, respectively.

[0455] In the exposure treatment in step (vi), the fourth composition layer is irradiated with light via a mask having a light-transmitting portion and a light-shielding portion. Light is incident on the fourth composition layer (exposure portion) through the light-transmitting portion, but is not incident on the fourth composition layer (non-exposure portion) because it cannot pass through the light-shielding portion. Therefore, an exposure portion and a non-exposure portion corresponding to the light-transmitting portion and the light-shielding portion of the mask can be provided on the fourth composition layer. The mask can be in close contact with the fourth composition layer (contact exposure method), or it can be non-closed and exposed using parallel light (non-contact exposure method), which is the same as step (IV) in the first embodiment.

[0456] By the development treatment in step (vii), the exposed portion of the fourth composition layer is not removed, but the non-exposed portion of the fourth composition layer is removed. The exposed portion of the fourth composition layer remaining after development has the same shape as the light-transmitting portion of the mask (mask pattern), and can function as a resist layer (hereinafter, sometimes referred to as a "resist pattern").

[0457] In step (viii), a pattern is formed on the second composition layer. In step (viii), etching is performed using the resist pattern formed in steps (vi) and (vii) as a mask to form a pattern corresponding to the core layer on the second composition layer. The etching method can be performed by a known method such as dry etching using a plasma gas and wet etching using an etchant (etching liquid), preferably dry etching using a plasma gas.

[0458] The plasma treatment can be carried out by treating the surface of the second composition layer exposed through the resist pattern (fourth composition layer) in a plasma generated by introducing a gas into a plasma generator. Examples of the plasma generation method include microwave plasma using microwaves, high-frequency plasma using high frequencies, atmospheric pressure plasma generated under atmospheric pressure, vacuum plasma generated under vacuum, and the like, preferably vacuum plasma generated under vacuum.

[0459] The plasma-generating gas is not particularly limited, and for example, SF 6 , Ar, O 2 In addition, the time of the plasma treatment is not particularly limited, and is preferably appropriately set according to the thickness of the second composition layer and the fourth composition layer.

[0460] When plasma gas is used to implement step (viii), the resist pattern (fourth composition layer) can also be removed during the process of forming a pattern on the second composition layer. The fourth composition layer is not completely removed and sometimes remains on the second composition layer, but in the case described above, the step (ix) of removing the fourth composition layer can also be implemented. The method for removing the fourth composition layer is preferably appropriately set according to the composition of the resist composition contained in the fourth composition layer. For example, the fourth composition layer can be removed using an alkaline stripping solution such as a sodium hydroxide solution.

[0461] In the method for producing an optical waveguide according to the second embodiment, by performing steps (iv) to (viii) (including step (ix) as necessary), a core layer as a cured second composition layer is obtained on the lower cladding layer.

[0462] The step (x) and the step (xi) in the second embodiment can be carried out in the same manner as the step (VII) and the step (VIII) in the first embodiment, respectively, for example.

[0463] [Photoelectric hybrid substrate and method for manufacturing the same]

[0464] An optoelectronic hybrid substrate according to one embodiment of the present invention includes the above-mentioned optical waveguide. Generally, the optoelectronic hybrid substrate includes an optical waveguide and a circuit substrate. The circuit substrate may include electronic components and wiring connected to the electronic components. As electronic components, for example, passive components such as capacitors, inductors, resistors, and active components such as semiconductor chips, etc. In addition, the optical waveguide and the wiring of the circuit substrate may be connected via a photoelectric conversion element. The photoelectric conversion element may include a combination of a light-emitting element that can convert electricity into light (for example, a surface-emitting light-emitting diode) and a light-receiving element that can convert light into electricity (for example, a photodiode). In addition, the optoelectronic hybrid substrate may also include optical elements such as reflectors in order to adjust the optical path.

[0465] As an example of a preferred optoelectronic hybrid substrate, there can be cited a substrate having a chip with an optical integrated circuit formed on a silicon wafer. The chip is expected to be put into practical use early using silicon photonics, for example, it is expected to be installed in a semiconductor package. The optoelectronic hybrid substrate having the chip includes, for example, a circuit substrate, a chip mounted on the circuit substrate, and an optical waveguide. The optical waveguide can be used to connect the wiring of the circuit substrate and the chip, or to connect multiple chips.

[0466] In chips made of silicon photonics, light with wavelengths of 1310nm and 1550nm is usually used, and 1310nm is the mainstream (Sho Yoshida, Daisuke Suganuma, Takaaki Ishiba, "Fabrication and Loss Reduction of Single-Mode Polymer Waveguides Based on Mosquito Method", 28th Spring Lecture Meeting of the Japan Electronics Installation Society, 2014). Therefore, the optical waveguide is preferably capable of transmitting light of 1310nm and 1550nm or wavelengths close thereto, for example, preferably capable of transmitting light of wavelengths of 1300nm to 1320nm. The optical waveguide involved in the above-mentioned embodiment can transmit light of these wavelengths.

[0467] Generally, between single-mode and multi-mode, single-mode can achieve faster transmission. Therefore, from the viewpoint of high-speed transmission, single-mode optical waveguides are preferred as optical waveguides used in optoelectronic hybrid circuits. In single-mode optical waveguides, the width of the core layer is preferably small. For example, it is preferred to form a core layer with a width of less than 10 μm or less than 5 μm. In addition, an optical waveguide having such a small core layer is also preferred from the viewpoint of increasing the design freedom of the package when the optical waveguide is applied to a semiconductor package. According to the optical waveguide involved in the above-mentioned embodiment, the width of the core layer can be reduced as described above.

[0468] Since the opto-electric hybrid substrate includes the above-mentioned optical waveguide, the method for manufacturing the opto-electric hybrid substrate includes the same method as the method for manufacturing the optical waveguide.

[0469] Example

[0470] The present invention is specifically described below by way of examples, but the present invention is not limited to these examples. It should be noted that, in the following description, unless otherwise expressly stated, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass", respectively. The temperature condition where the temperature is not particularly specified is room temperature (23° C.), and the pressure condition where the pressure is not particularly specified is atmospheric pressure (1 atm).

[0471] <Example I: Example of resin sheet>

[0472] <Synthesis Example 1: Synthesis of an acid-modified epoxy acrylate resin containing a naphthol aralkyl skeleton>

[0473] 325 parts of an epoxy resin having a naphthol aralkyl skeleton ("ESN-475V", manufactured by Nippon Steel Chemical Materials Co., Ltd.) with an epoxy equivalent of 330 g / eq. were placed in a flask equipped with a gas inlet pipe, a stirring device, a cooling tube and a thermometer, and 340 parts of propylene glycol monomethyl ether were added, heated to dissolve, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated to 95-105°C, 72 parts of acrylic acid were slowly added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90°C, 130 parts of tetrahydrophthalic anhydride were added, the mixture was reacted for 8 hours, and the mixture was cooled. The solvent was removed to obtain an acid-modified epoxy acrylate resin having an acid value of 90 mgKOH / g and a non-volatile component of 70% by mass. The weight average molecular weight (Mw) of the obtained acid-modified epoxy acrylate resin was 1,000.

[0474] <Manufacturing Example I-1: Manufacture of resin sheet>

[0475] (1) Preparation of varnish-like resin composition

[0476] 20 parts of the naphthol aralkyl skeleton-containing ester-type acid-modified epoxy acrylate resin obtained in Synthesis Example 1, 10 parts of naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd., epoxy equivalent of about 330 g / eq.), 5 parts of naphthalene-type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent of about 170 g / eq.), 12.5 parts of photocurable resin ("DPHA" manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate), 1.5 parts of photopolymerization initiator ("Omnirad 379EG" manufactured by IGM Co., Ltd.), 0.1 parts of alkoxysilane compound ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.), 0.1 parts of curing accelerator ("CUREZOL 600" manufactured by Shikoku Chemical Industry Co., Ltd.), were mixed. C11Z-A", 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine), 15 parts of methyl ethyl ketone and 1.5 parts of propylene glycol monomethyl ether acetate were mixed with a high-speed rotary mixer to prepare a varnish-like resin composition.

[0477] (2) Manufacturing of resin sheets

[0478] A polyethylene terephthalate film ("Lumirror T6AM" manufactured by Toray Industries, thickness 38 μm, softening point 130°C) was prepared as a support. The varnish-like resin composition prepared above was uniformly applied to the support using a die coater so that the thickness of the dried resin composition layer was 5 μm, 6.5 μm, 7 μm, 10 μm, 20 μm or 50 μm, and dried at 80°C to 110°C (maximum temperature 110°C) for 7 minutes to form a resin composition layer. Then, a protective film (biaxially stretched polypropylene film, "MA-411" manufactured by Oji F-Tex) was placed on the surface of the resin composition layer and laminated at 80°C to produce a resin sheet having a three-layer structure of support / resin composition layer / protective film.

[0479] <Production Examples I-2 to I-14: Production of Resin Compositions and Resin Sheets>

[0480] The resin composition was prepared in the same manner as in Manufacturing Example I-1 except that the components were mixed in the blending composition shown in Table 1, and a resin sheet was produced. It should be noted that in the table, the blending amount of each component refers to parts by mass, which is the actual amount used. It should be noted that in Table 1, the meanings of the abbreviations are as follows.

[0481] (A) Carboxyl-containing resins

[0482] "Synthesis Example 1": Acid-modified epoxy acrylate resin containing a naphthol aralkyl skeleton synthesized in Synthesis Example 1 (acid value 90 mgKOH / g, Mw: 1,000), non-volatile content 70% by mass

[0483] (B) Epoxy resin

[0484] · "HP-4710": Made by DIC Corporation, naphthalene-based tetrafunctional epoxy resin, epoxy equivalent weight about 170 g / eq.

[0485] "ESN-475V": Made by Nippon Steel Chemicals Co., Ltd., naphthol aralkyl skeleton epoxy resin, epoxy equivalent weight about 330g / eq.

[0486] (C) Photocurable resin

[0487] "DPHA": Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

[0488] (D) Photopolymerization initiator

[0489] · "Omnirad 379EG": manufactured by IGM, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one

[0490] (E) Alkoxysilane compound

[0491] "KBM-403": Made by Shin-Etsu Chemical Co., Ltd., 3-glycidyloxypropyltrimethoxysilane

[0492] "KBM-4803": Made by Shin-Etsu Chemical Co., Ltd., 8-glycidyloxyoctyltrimethoxysilane

[0493] "KBM-1003": Made by Shin-Etsu Chemical Co., Ltd., vinyl trimethoxysilane

[0494] "KBM-5803": Made by Shin-Etsu Chemical Co., Ltd., 8-methacryloyloxyoctyltrimethoxysilane

[0495] "KBM-5103": Made by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane

[0496] "KBM-573": Made by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane

[0497] (E') Silane compound not having an alkoxysilyl group

[0498] "KF-105": manufactured by Shin-Etsu Chemical Co., Ltd., epoxy-modified silicone oil

[0499] (F) Curing accelerator

[0500] · "C11Z-A": Made by Shikoku Chemical Industry Co., Ltd., 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine

[0501] (H) Organic solvents

[0502] "MEK": methyl ethyl ketone

[0503] "PGMEA": Propylene glycol monomethyl ether acetate

[0504] <Test Example 1: Measurement of refractive index of cured product of resin composition using resin sheet>

[0505] The refractive index of the cured product of the resin composition used for producing the resin sheet was measured by the following method.

[0506] The protective film was peeled off from the resin sheet having a resin composition layer with a thickness of 6.5 μm manufactured in each manufacturing example. Thereafter, the resin sheet was laminated on a 6-inch silicon wafer at 80°C, and the support was peeled off to form a resin composition layer with a thickness of 6.5 μm on the silicon wafer. Thereafter, the resin composition layer was exposed to an optimal exposure amount of 5000 mJ using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.). After exposure, a 1.0 mass % tetramethylammonium hydroxide aqueous solution at 23°C was used as a developer, and spray development was performed on the resin composition layer at a spray pressure of 0.1 MPa for 30 seconds. After spray development, the resin composition layer was subjected to 3J / cm 2 The sample was irradiated with ultraviolet light and then heated at 190°C for 90 minutes in a nitrogen atmosphere to obtain a sample formed of a cured product of the resin composition. The refractive index n (1310 nm) of the obtained sample was measured at room temperature and atmospheric pressure using a 2010M prism coupler (manufactured by Metricon) and a 1310 nm laser.

[0507] <Test Example 2: Measurement of shrinkage ratio>

[0508] The protective film was peeled off from the resin sheet with a resin composition layer having a thickness of 10 μm manufactured in each manufacturing example. The resin sheet was arranged on a 6-inch silicon wafer in such a way that the resin composition layer was in contact with the silicon wafer, and laminated using a vacuum laminator ("VP160" manufactured by Nikko-Materials). The lamination conditions were: 30 seconds for vacuuming, 60°C for pressing temperature, 0.3MPa for pressing pressure, and 30 seconds for pressing time. Afterwards, the support was peeled off to obtain a laminate A having a silicon wafer and a resin composition layer.

[0509] Using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.), the resin composition layer of the obtained laminate A was exposed to ultraviolet light at an exposure energy of 8 to 10 levels of gloss residual stages on a 41-level step exposure meter. The exposure was performed using a quartz glass mask having a mask pattern that can depict multiple straight lines with a length of 5 cm at L / S (line / space) = 5μm / 100μm. In the L / S of the quartz glass mask, the line is equivalent to the width of the core layer, and the space is equivalent to the space between the core layers. After exposure, after standing at room temperature for 30 minutes, a 1 mass % sodium carbonate aqueous solution at 30°C as a developer was sprayed on the entire surface of the resin composition layer at a spray pressure of 0.2MPa for 1 minute. After spray development, 2J / cm 2The wafer was cut in a direction perpendicular to the core wire, and the cross section was observed under a microscope. The area α was calculated by measuring the longitudinal and transverse lengths of the rectangular core. After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 69 minutes to cure the resin composition layer. After the resin composition layer was cured, the same cross section was observed under a microscope, and the area β was calculated by measuring the longitudinal and transverse lengths of the rectangular core. Using the calculated areas α and β, the shrinkage rate c (c = β / α) was calculated.

[0510] The amounts of raw materials used to prepare the resin compositions of the respective Production Examples and the measurement results of the Test Examples are shown in Table 1 below.

[0511] [Table 1]

[0512]

[0513] <Example I-1: Formation of optical waveguide>

[0514] The sheets produced in Production Example I-1 and Production Example I-2 were prepared, and the resolution, adhesion to the base layer, and light transmission loss were evaluated by the following methods.

[0515] <Test Example 3: Evaluation of resolution (thin-line waveguide formability)>

[0516] The copper layer of the glass epoxy substrate (copper-clad laminate) having a copper layer with a thickness of 18 μm was roughened using a surface treatment agent (CZ8100, manufactured by MEC) containing an organic acid to prepare a substrate. Next, the protective film was peeled off from the resin sheet having a resin composition layer with a thickness of 10 μm manufactured in Manufacturing Example I-2. The resin sheet was arranged on the copper-clad laminate in such a way that the resin composition layer of the resin sheet was in contact with the copper-clad laminate, and laminated using a vacuum laminator ("VP160" manufactured by Nikko-Materials). The lamination conditions were: 30 seconds for vacuuming, 60°C for crimping temperature, 0.3MPa for crimping pressure, and 30 seconds for pressing time. Afterwards, the support was peeled off, and ultraviolet exposure was performed using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) with an exposure energy of 8 levels of gloss residual stages of a 41-level stage exposure meter. The exposure was performed without using a quartz glass mask. After exposure, 2J / cm 2 After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resin composition layer. The lower coating layer was formed by curing the resin composition layer, and an intermediate laminate B1 having a copper-clad laminate and a lower coating layer was obtained.

[0517] Next, the protective film was peeled off from the resin sheet with a thickness of 5 μm manufactured in Manufacturing Example I-1. A resin sheet was arranged on the lower coating layer in such a way that the resin composition layer of the resin sheet was in contact with the lower coating layer of the intermediate laminate B1, and a vacuum laminator ("VP160" manufactured by Nikko-Materials) was used for lamination to form a resin composition layer on the lower coating layer. The lamination conditions were: 30 seconds for vacuuming, 60°C for crimping temperature, 0.3MPa for crimping pressure, and 30 seconds for pressing time. Thus, a laminate B2 having a copper-clad laminate, a lower coating layer and a resin sheet was obtained in sequence. Afterwards, the support was peeled off to expose the resin composition layer.

[0518] Using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.), the resin composition layer of the laminate B2 was exposed to ultraviolet light at an exposure energy of 8 levels of gloss residual stages on a 41-level step exposure meter. The exposure was performed using a quartz glass mask having a mask pattern with straight lines drawn at L / S (line / space) = 5μm / 5μm. After exposure, the support was peeled off after standing at room temperature for 30 minutes. On the entire surface of the resin composition layer, a 1 mass % sodium carbonate aqueous solution at 30°C as a developer was sprayed at a spray pressure of 0.2MPa for 1 minute. After spray development, 2J / cm 2 The sample B3 was obtained by irradiating the sample with ultraviolet light and then heating it at 190°C for 1 hour in a nitrogen atmosphere, thereby obtaining a copper-clad laminate, a lower covering layer and a 5 μm thick wire layer (a layer formed by a cured product of the resin composition) in this order.

[0519] In addition, the same operation as above was performed except that the thickness of the resin sheet manufactured in Manufacturing Example I-1 was changed to 7 μm and a quartz glass mask having a mask pattern in which straight lines were drawn at L / S (line / space) = 7 μm / 7 μm was used, thereby obtaining a sample B4 having a copper-clad laminate, a lower cladding layer, and a 7 μm-thick line layer (a layer formed of a cured product of the resin composition) in this order. Furthermore, the same operation as above was performed except that the thickness of the resin sheet manufactured in Manufacturing Example I-1 was changed to 50 μm and a quartz glass mask having a mask pattern in which straight lines were drawn at L / S (line / space) = 50 μm / 50 μm was used, thereby obtaining a sample B5 having a copper-clad laminate, a lower cladding layer, and a 50 μm-thick line layer (a layer formed of a cured product of the resin composition) in this order.

[0520] The obtained samples B3, B4, and B5 were observed with a scanning electron microscope (SEM) (magnification: 2000 times). The resolution was evaluated according to the following evaluation criteria. The line width represents the width of the line layer.

[0521] Evaluation Benchmarks

[0522] “∘”: A line having a thickness of 5 μm and a line width of 5 μm can be formed, a line having a thickness of 7 μm and a line width of 7 μm can be formed, and a line having a thickness of 50 μm and a line width of 50 μm can be formed.

[0523] “Δ”: A line having a thickness of 5 μm and a line width of 5 μm could not be formed, but a line having a thickness of 7 μm and a line width of 7 μm or a line having a thickness of 50 μm and a line width of 50 μm could be formed.

[0524] “×”: A line having a thickness of 5 μm and a line width of 5 μm, a line having a thickness of 7 μm and a line width of 7 μm, and a line having a thickness of 50 μm and a line width of 50 μm could not be formed.

[0525] <Test Example 4: Evaluation of Adhesion to Base Layer>

[0526] 60 parts of an acid-modified epoxy acrylate resin containing a cresol novolac skeleton ("CCR-1171H" manufactured by Nippon Kayaku Co., Ltd.), 20 parts of a biphenyl type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation), 40 parts of a photocurable resin ("DPHA" manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate), 2.0 parts of a photopolymerization initiator ("Omnipol 379" manufactured by IGM Co., Ltd.), 4.0 parts of melamine, 25 parts of barium sulfate ("BARIACE B-30" manufactured by Sakai Chemical Co., Ltd.), and 2 parts of a green pigment ("CG5370" manufactured by Dainichi Seika Co., Ltd.) were added, and methyl ethyl ketone was added so that the non-volatile component concentration became 60% by mass, and a varnish-like resin composition was prepared using a high-speed rotary mixer.

[0527] A polyethylene terephthalate film ("Lumirror T6AM" manufactured by Toray Industries, thickness 38 μm, softening point 130°C) was prepared as a support. The varnish-like resin composition prepared above was evenly applied to the support using a die coater to make the thickness of the dried resin composition layer 25 μm, and dried at 75°C to 110°C for 10 minutes to form a resin composition layer. Through these operations, a resin sheet containing a photosensitive solder resist layer was obtained.

[0528] The copper layer of a glass epoxy substrate (copper-clad laminate) having a copper layer with a thickness of 18 μm was roughened using a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC) to prepare a substrate. A resin sheet was arranged on the copper-clad laminate in such a way that the solder resist layer was in contact with the copper-clad laminate of the substrate, and laminated using a vacuum laminator ("VP160" manufactured by Nikko-Materials). The lamination conditions were: 30 seconds for vacuuming, 60°C for crimping temperature, 0.3 MPa for crimping pressure, and 30 seconds for pressing time. After that, the support was peeled off, and ultraviolet exposure was performed using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) with an exposure energy of 8 levels of gloss residual stages of a 41-level step exposure meter. The exposure was performed without using a quartz glass mask. After leaving the photosensitive resin composition at room temperature for 30 minutes after exposure, the unexposed portion was spray-developed with a 1 mass % sodium carbonate aqueous solution at 30° C. for 60 seconds at 2 J / cm 2 After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the solder resist layer, thereby obtaining a base evaluation substrate C1.

[0529] The protective film was peeled off from the resin sheet having a resin composition layer with a thickness of 10 μm manufactured in Manufacturing Example I-2. The resin sheet was arranged on the solder resist layer in such a way that the resin composition layer of the resin sheet was in contact with the solder resist layer of the underlying evaluation substrate C1, and laminated using a vacuum laminator ("VP160" manufactured by Nikko-Materials). The lamination conditions were: vacuuming time of 30 seconds, crimping temperature of 60°C, crimping pressure of 0.3 MPa, and pressurization time of 30 seconds. After that, the support was peeled off, and ultraviolet exposure was performed using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) with an exposure energy of 8 levels of gloss residual stages on a 41-level step exposure meter. The exposure was performed without using a quartz glass mask. After exposure, 2 J / cm 2 After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resin composition layer, thereby obtaining a bottom evaluation substrate C2. Next, the obtained bottom evaluation substrate C2 was placed under HAST conditions (130°C, 85% RH) for 100 hours. After that, it was returned to room temperature, and a cross-cut (1 mm square grid-shaped incision) was performed on the surface of the resin composition layer to confirm whether there were defects in the resin composition layer.

[0530] The case where the resin composition layer and the substrate were not peeled off and no defect occurred in the resin composition layer after cross cutting was rated as "○", and the case where the interface between the resin composition layer and the substrate was peeled off and a defect occurred in the resin composition layer after cross cutting was rated as "×".

[0531] <Test Example 5: Evaluation of the difference in shrinkage between the core layer and the cladding layer>

[0532] In each of the Examples and Comparative Examples, the shrinkage ratio c of the core layer resin composition was calculated. core The shrinkage of the resin composition for the coating layer c clad The absolute value d (d = |c clad -c core |).

[0533] <Test Example 6: Measurement of optical transmission loss>

[0534] (1-1. Formation of Lower Coating Layer)

[0535] The copper layer of a glass epoxy substrate (copper-clad laminate) having a copper layer of 18 μm in thickness was roughened using a surface treatment agent (CZ8100, manufactured by MEC) containing an organic acid to prepare a substrate. The protective film was peeled off from the resin sheet having a resin composition layer of 10 μm in thickness manufactured in Manufacturing Example I-2. The resin sheet was arranged on the copper-clad laminate in such a way that the resin composition layer of the resin sheet was in contact with the copper-clad laminate of the substrate, and laminated using a vacuum laminator ("VP160" manufactured by Nikko-Materials). The lamination conditions were: 30 seconds for vacuuming, 60°C for crimping temperature, 0.3MPa for crimping pressure, and 30 seconds for pressing time. Afterwards, the support was peeled off, and ultraviolet exposure was performed using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) with an exposure energy of 8 levels of gloss residual stages of a 41-level step exposure meter. The exposure was performed without using a quartz glass mask. After exposure, 2J / cm 2 After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resin composition layer. The lower coating layer was formed by curing the resin composition layer, and an intermediate laminate D1 having a copper-clad laminate and a lower coating layer was obtained.

[0536] (1-2. Formation of core layer)

[0537] The protective film was peeled off from the resin sheet having a resin composition layer with a thickness of 5 μm manufactured in Manufacturing Example I-1. The resin sheet was arranged on the surface of the lower coating layer of the intermediate laminate D1 in such a way that the resin composition layer of the resin sheet was in contact with the lower coating layer of the intermediate laminate D1, and laminated using a vacuum laminator ("VP160" manufactured by Nikko-Materials). The lamination conditions were: vacuuming time of 30 seconds, crimping temperature of 60°C, crimping pressure of 0.3 MPa, and pressing time of 30 seconds. After that, the support was peeled off, and ultraviolet exposure was performed using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) with an exposure energy of 8 levels of gloss residual stages of a 41-level step exposure meter. The exposure was performed using a quartz glass mask having a mask pattern that can depict multiple straight lines with a length of 5 cm at L / S (line / space) = 5 μm / 100 μm. In the L / S of the quartz glass mask, the line is equivalent to the width of the core layer, and the interval is equivalent to the interval between the core layers. After exposure, the support was peeled off after standing at room temperature for 30 minutes, and a 1 mass % tetramethylammonium aqueous solution at 23°C as a developer was sprayed on the entire surface of the resin composition layer at a spray pressure of 0.2 MPa for 1 minute. After spray development, 2 J / cm 2 After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resin composition layer. The core layer was formed by curing the resin composition layer, and an intermediate laminate D2 having a copper-clad laminate, a lower cladding layer, and a core layer was obtained in sequence.

[0538] (1-3. Formation of upper cladding layer)

[0539] The protective film was peeled off from the resin sheet having a resin composition layer with a thickness of 20 μm manufactured in Manufacturing Example I-2. The resin sheet was arranged on the core layer of the intermediate laminate D2 in such a manner that the resin composition layer of the resin sheet was in contact with the core layer of the intermediate laminate D2, and laminated using an intermittent vacuum pressurizing laminator (manufactured by Nikko-Materials, a two-stage laminating laminator, CVP700). The laminating conditions were: vacuuming time of 30 seconds, pressing temperature of 60°C, pressing pressure of 0.3 MPa, and pressing time of 30 seconds. After that, the support was peeled off, and ultraviolet exposure was performed using a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) with an exposure energy of 8 levels of gloss residual stages on a 41-level stage exposure meter. The exposure was performed without using a quartz glass mask. After exposure, 2 J / cm 2After that, it was placed in a clean oven and heated from room temperature to 170°C. After reaching 170°C, it was heated for 60 minutes in a nitrogen atmosphere to cure the resin composition layer. The upper coating layer was formed by curing the resin composition layer, and a sample laminate D3 having a copper-clad laminate, a lower coating layer, a core layer, and an upper coating layer was obtained in this order.

[0540] In the sample laminate D3, the combination of the lower cladding layer and the upper cladding layer constitutes a cladding layer. Therefore, an optical waveguide including the cladding layer and the core layer located in the cladding layer is obtained. In addition, in the sample laminate D3, the core layer has a linear pattern corresponding to the mask pattern of the quartz glass mask and having a length of 5 cm, and the width (line width) and spacing (space) of the core layer contained in these patterns are consistent with the width (line width) and spacing (space) of the mask pattern.

[0541] (2. Preparation of test substrate)

[0542] From the sample laminate D3 produced by the above operation, the portion where the core layer was formed, that is, the core layer where a 5 cm straight line pattern was drawn and the surrounding cladding layer were cut to obtain a test substrate D4 having an optical transmission path. The cutting conditions were as follows.

[0543] Cutting device: DAD3221 (manufactured by DISCO)

[0544] Blade: ZH14-SD4000-VI-50

[0545] Spindle speed: 30K / min

[0546] Cutting speed: 5mm / sec

[0547] Blade height: 0.060mm

[0548] Dicing tape: T-80W (manufactured by Denka, 80umt)

[0549] (3-1. Measurement of light transmission loss of calibration optical system)

[0550] As described later, the transmission loss of the optical system composed of the test substrate D4 and the focusing module was measured from the transmission loss measurement optical system of the test substrate D4. That is, on the vibration-isolating table covered by the dark curtain, the light source (1310nm light source, "LPSC-1310-FC" manufactured by THORLABS) and the light receiver (optical power meter "N7742" manufactured by Keysight) were connected via an optical fiber (incident optical fiber) to obtain an optical system for calibration. The light source was made to emit light, and the intensity of the light entering the light receiver was measured by the light receiver to measure the loss of the optical system for calibration.

[0551] (3-2. Measurement of optical transmission loss)

[0552] A test substrate D4 is set on a vibration-isolating table covered with a dark curtain. A focusing module (numerical aperture 0.18) is connected to one end (incident end) of the optical waveguide of the test substrate D4, and a light source (1310nm light source, "LPSC-1310-FC" manufactured by THORLABS) is connected to the focusing module via an optical fiber (incident optical fiber). In addition, another focusing module (numerical aperture 0.18) is connected to the other end (exit end) of the optical waveguide of the test substrate D4, and a light receiver (optical power meter "N7742" manufactured by Keysight) is connected to the focusing module via an optical fiber (exit optical fiber). Through the above operations, after the light emitted from the light source passes through the optical fiber (incident optical fiber), focusing module, optical waveguide, focusing module and optical fiber (exit optical fiber) in sequence, an optical system is obtained that enters the light receiver. Hereinafter, this optical system is sometimes referred to as the "sample optical system". The light source was made to emit light, and the intensity of the light entering the light receiver was measured using the light receiver, thereby measuring the loss of the sample optical system.

[0553] The loss of the optical waveguide included in the test substrate D4 was calculated by subtracting the loss of the correction optical system from the loss of the sample optical system.

[0554] (3-3. Measurement of Light Transmission Loss (dB / cm) of Optical Waveguide Before Reliability Test)

[0555] After the loss measurement of the above-mentioned optical waveguide with a length of 5 cm was completed, the optical waveguide was cut into 4 cm and the same measurement was performed. Moreover, by repeating the cutting of the optical waveguide into 3 cm and the measurement, the measurement values ​​were calculated for the optical waveguide with a length of 5 cm, the optical waveguide with a length of 4 cm, and the optical waveguide with a length of 3 cm, respectively. Then, the measurement results were plotted in a coordinate system with the length of the optical waveguide as the horizontal axis and the loss of the optical waveguide as the vertical axis, and the coordinates of three points representing the measurement results were obtained. The approximate straight line of these three points was calculated by the least squares method, and the slope of the approximate straight line was obtained as the loss per unit distance of the optical waveguide (optical transmission loss). The calculated value of the optical transmission loss was evaluated according to the following evaluation criteria.

[0556] Evaluation Benchmarks

[0557] “◎”: The optical transmission loss value is less than 0.4dB / cm;

[0558] “○”: The optical transmission loss value is 0.4 dB / cm or more and less than 0.5 dB / cm;

[0559] “△”: The optical transmission loss is greater than 0.5 dB / cm and less than 1.0 dB / cm;

[0560] “×”: The value of the optical transmission loss is 1.0 dB / cm or more.

[0561] (4. Measurement of optical transmission loss (dB / cm) of optical waveguide after heat and humidity resistance test (HAST test))

[0562] Separately from the test substrate D4 used in the above, a test substrate D5 was prepared in the same steps. The test substrate D5 was placed in a high temperature constant humidity tester set at 130°C and 85% RH for 100 hours, and the above-mentioned operations 3-1. to 3-3. were performed, thereby calculating the value of the transmission loss after the heat and humidity test (HAST test). Furthermore, the change rate (%) of the calculated value of the optical transmission loss after the heat test (HAST test) compared with the value of the optical transmission loss before the test was calculated, and evaluated according to the following evaluation criteria.

[0563] Evaluation Benchmarks

[0564] “◎”: The change rate is less than 20%;

[0565] “○”: The change rate is 20% or more and less than 30%;

[0566] “△”: The change rate is greater than 30% and less than 50%;

[0567] “×”: The change rate is 50% or more.

[0568] <Test Example 7: Confirmation of Pattern>

[0569] For the test substrate D4, the light receiver was removed and an infrared camera (InGaAs camera with a 100x objective lens) was installed instead. The light source was illuminated, and the infrared camera was used to capture the light emitted from the end of the optical fiber (exit optical fiber). When only one circular edge of light was observed, it was determined to be single-mode. In addition, when multiple edges of light were observed, it was determined to be multi-mode.

[0570] <Examples I-2 to I-10 and Comparative Examples I-1 to I-3: Formation of Optical Waveguide>

[0571] As shown in Table 2, an optical waveguide was formed in the same manner as in Example I-1 except that the combination of the core resin composition and the cladding resin composition was changed, and evaluation was performed by various tests.

[0572] The combinations of the core resin composition and the covering resin composition used in the respective Examples and Comparative Examples and the evaluation results are shown in the following Table 2. In the following Table 2, the abbreviations have the following meanings.

[0573] NA: Numerical aperture of the optical waveguide (the numerical aperture NA is a value expressed by the following formula (1))

[0574]

[0575] "S" in the Mode column: Single mode

[0576] "M" in the Mode column: Multimode

[0577] [Table 2]

[0578]

[0579] <Example II: Example of resin ink>

[0580] <Production Example II-1: Production of resin composition>

[0581] 10 parts of a resin containing an epoxy group and a radical polymerizable group ("EBECRYL 3605" manufactured by Daicel Allnex, epoxy equivalent of 450 g / eq., bisphenol A type epoxy semiacrylate), 4 parts of a naphthol aralkyl skeleton epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd., epoxy equivalent of about 330 g / eq.), 1 part of a naphthalene type epoxy resin ("HP-4032SS" manufactured by DIC, epoxy equivalent of about 145 g / eq.), 3 parts of an alkylphenol type epoxy resin ("HP-820" manufactured by DIC, epoxy equivalent of about 225 g / eq.), 10 parts of a photocurable resin ("DPHA" manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate), and 0.1 parts of a photopolymerization initiator ("Irgacure A resin composition (resin ink) was prepared by using a high-speed rotary mixer.

[0582] <Production Examples II-2 to II-8: Production of Resin Compositions>

[0583] A resin composition was prepared in the same manner as in Production Example II-1 except that the components were mixed in the blending composition shown in Table 3. In addition, the abbreviations in Table 3 have the following meanings.

[0584] (A) Resins containing epoxy groups and free radical polymerizable groups

[0585] · "EBECRYL 3605": manufactured by Daicel Allnex, bisphenol A epoxy semi-acrylate, epoxy equivalent 450g / eq.

[0586] (B) Epoxy resin

[0587] · "HP-4032SS": Made by DIC Corporation, naphthalene-based epoxy resin, epoxy equivalent weight about 145 g / eq.

[0588] · "HP-820": manufactured by DIC Corporation, alkylphenol type epoxy resin, epoxy equivalent weight about 225g / eq.

[0589] "ESN-475V": Made by Nippon Steel Chemicals Co., Ltd., naphthol aralkyl skeleton epoxy resin, epoxy equivalent weight about 330g / eq.

[0590] (C) Photocurable resin

[0591] "DPHA": Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

[0592] (D) Photopolymerization initiator

[0593] · "Irgacure OXE-01": manufactured by BASF, 2-(Benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone

[0594] (E) Alkoxysilane compound

[0595] "KBM-403": Made by Shin-Etsu Chemical Co., Ltd., 3-glycidyloxypropyltrimethoxysilane

[0596] "KBM-4803": Made by Shin-Etsu Chemical Co., Ltd., 8-glycidyloxyoctyltrimethoxysilane

[0597] "KBM-1003": Made by Shin-Etsu Chemical Co., Ltd., vinyl trimethoxysilane

[0598] "KBM-5803": Made by Shin-Etsu Chemical Co., Ltd., 8-methacryloyloxyoctyltrimethoxysilane

[0599] <Test Example 8: Measurement of Refractive Index of Cured Product of Resin Composition Using Resin Ink>

[0600] The refractive index of a cured product of a resin composition using the resin ink was measured by the following method.

[0601] After adding 1.5 parts of propylene glycol monomethyl ether acetate to the resin ink prepared in each manufacturing example, the resin ink was spin-coated on a 6-inch silicon wafer and heated at 100° C. for 3 minutes, thereby forming a 6.5 μm thick resin composition layer on the silicon wafer. Thereafter, the resin composition layer was subjected to a 3 J / cm 2 The sample was irradiated with ultraviolet rays, placed in a clean oven, heated from room temperature to 190°C, and then heated for 90 minutes in a nitrogen atmosphere after reaching 190°C to obtain a sample formed of a cured product of the resin composition. The refractive index n (1310 nm) of the obtained sample was measured at room temperature and atmospheric pressure using a 1310 nm laser using a 2010M prism coupler (manufactured by Metricon).

[0602] <Test Example 9: Measurement of shrinkage ratio>

[0603] After adding 1.5 parts of propylene glycol monomethyl ether acetate to the resin ink prepared in each manufacturing example, the resin ink was spin-coated on a 6-inch silicon wafer and heated at 100°C for 3 minutes to form a 10 μm thick resin composition layer on the silicon wafer. 2The resin composition layer was irradiated with ultraviolet light, placed in a clean oven, and heated from room temperature to 190°C. After reaching 190°C, a heat treatment was performed for 90 minutes to cure the resin composition layer. Next, a resist material ("THMR-iP5700HP" manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the cured resin composition layer and spin-coated at 1500rpm for 30 seconds to form a resist layer with a thickness of 10μm. Then, it was heated on a hot plate heated to 110°C for 90 seconds, and a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) was used to perform ultraviolet exposure with an exposure energy of 8 to 10 levels of gloss residual levels of a 41-level step exposure meter. The exposure was performed using a quartz glass mask having a mask pattern that can depict multiple straight lines with a length of 5cm at L / S (line / space) = 5μm / 100μm. In the L / S of the quartz glass mask, the line is equivalent to the width of the core layer, and the space is equivalent to the space between the core layers. After that, it was put into a clean oven, heated from room temperature to 190°C, and after reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resist layer. After that, after the resist layer was developed to form a resist pattern, a plasma device ("PR-200" manufactured by Yamato Scientific Co., Ltd.) was used to etch the resist pattern and the resin composition layer exposed through the resist pattern to form a pattern of the core layer. The wafer was cut in a direction perpendicular to the obtained core wire, and the cross section at this time was observed under a microscope. The area α was calculated by measuring the vertical and horizontal lengths of the rectangular core. After that, it was put into a clean oven, heated from room temperature to 190°C, and after reaching 190°C, it was heated for 69 minutes. After the heat treatment, the same cross section was observed under a microscope, and the area β was calculated by measuring the vertical and horizontal lengths of the rectangular core. Using the calculated areas α and β, the shrinkage rate (c) was calculated in the same way as in Test Example 2.

[0604] <Test Example 10: Analysis of organic solvent in resin composition layer by GC / MS (gas chromatography mass spectrometry)>

[0605] 5 mg of the resin ink prepared in Manufacturing Examples II-1 to II-8 was weighed and treated with a GCMS-QP2020-NX (manufactured by Shimadzu Corporation) under oven conditions of 250°C for 10 minutes, and measured under conditions of a sample line temperature of 260°C, a transfer line temperature of 260°C, and a cycle time of 55 minutes. The type of solvent and volatile species were determined from each detected peak, and compared with a pre-prepared standard curve, thereby analyzing the content of organic solvents and volatile species contained in the sample.

[0606] <Test Example 11: Appearance during Curing>

[0607] 10 g of the resin ink prepared in Examples II-2 to II-5 and II-7 to II-8 was placed on an aluminum cap and allowed to stand under vacuum. After confirming that bubbles were fully discharged, a 2 J / cm 2 After that, it was placed in a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resin composition layer. The appearance of the obtained cured product was observed, and those with no bubbles observed were marked as "○", and those with bubbles observed were marked as "×".

[0608] The amounts of raw materials used to prepare the resin compositions of the respective Production Examples and the measurement results of the Test Examples are summarized in the following Table 3. In Table 3, the abbreviations have the following meanings.

[0609] · Residual organic solvent amount (mass %): the residual organic solvent amount (mass %) measured in Test Example 10

[0610] [Table 3]

[0611]

[0612] <Example II-1: Formation of optical waveguide>

[0613] The resin inks prepared in Production Examples II-1 and II-2 were prepared, and the same operations as in Test Examples 4 and 5 were performed to evaluate the adhesion to the base layer and the difference in shrinkage. In addition, the optical transmission loss was evaluated by the following method.

[0614] <Test Example 12: Measurement of optical transmission loss>

[0615] (1-1. Formation of Lower Coating Layer)

[0616] The copper layer of a glass epoxy substrate (copper-clad laminate) having a copper layer with a thickness of 18 μm was roughened using a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC) to prepare a substrate. The resin composition prepared in Manufacturing Example II-2 was evenly applied to the copper-clad laminate of the substrate using a bar coater to a thickness of 10 μm. Afterwards, 2 J / cm 2 The resin composition layer was cured by irradiating the resin composition layer with ultraviolet rays and placing the copper-clad laminate plate in a clean oven and heating the temperature from room temperature to 190°C. After reaching 190°C, the resin composition layer was cured by heating the copper-clad laminate plate for 90 minutes. The lower coating layer was formed by curing the resin composition layer, and an intermediate laminate E1 having a copper-clad laminate plate and a lower coating layer was obtained.

[0617] (1-2. Formation of core layer)

[0618] The resin composition prepared in Preparation Example II-1 was applied to the cover layer of the intermediate laminate E1 so that the thickness of the resin composition layer was 5 μm. 2 , put it into a clean oven, raise the temperature from room temperature to 190°C, and after reaching 190°C, heat it for 90 minutes to cure the resin composition layer. Next, apply a resist material ("THMR-iP5700HP" manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the cured resin composition layer and spin coat it at 1500rpm for 30 seconds to form a resist layer with a thickness of 10μm. Next, heat it on a hot plate heated to 110°C for 90 seconds, and use a projection exposure device ("UFX-2240" manufactured by Ushio Electric Co., Ltd.) to perform 250mJ of ultraviolet exposure. Exposure is performed using a quartz glass mask having a mask pattern that can depict multiple straight lines with a length of 5cm at L / S (line / space) = 5μm / 100μm. In the L / S of the quartz glass mask, the line is equivalent to the width of the core layer, and the space is equivalent to the space between the core layers. After that, it was put into a clean oven and heated from room temperature to 190°C. After reaching 190°C, it was heated for 90 minutes in a nitrogen atmosphere to cure the resist layer. After that, the resist layer was developed to form a resist pattern, and then a plasma device ("PR-200" manufactured by Yamato Scientific Co., Ltd.) was used to etch the resist pattern and the resin composition layer exposed through the resist pattern, thereby forming a pattern of the core layer. The core layer was formed by etching, and an intermediate laminate E2 having a copper-clad laminate, a lower cladding layer and a core layer in sequence was obtained.

[0619] (1-3. Formation of upper cladding layer)

[0620] The resin composition prepared in Preparation Example II-2 was applied to the core layer of the intermediate laminate E2 so that the thickness of the resin composition layer was 10 μm. 2 The resin composition layer was cured by irradiating the resin composition layer with ultraviolet rays and placing it in a clean oven, where the temperature was raised from room temperature to 190°C. After reaching 190°C, the resin composition layer was heated for 90 minutes to cure the resin composition layer. The upper coating layer was formed by curing the resin composition layer, and a sample laminate E3 having a copper-clad laminate, a lower coating layer, a core layer, and an upper coating layer was obtained in this order.

[0621] In the sample laminate E3, the combination of the lower cladding layer and the upper cladding layer constitutes a cladding layer. Therefore, an optical waveguide including the cladding layer and the core layer located in the cladding layer is obtained. In addition, in the sample laminate E3, the core layer has a linear pattern corresponding to the mask pattern of the quartz glass mask and having a length of 5 cm, and the width (line width) and spacing (space) of the core layer contained in these patterns are consistent with the width (line width) and spacing (space) of the mask pattern.

[0622] (2. Preparation of test substrate)

[0623] The same operation as 2. of Test Example 6 was performed except that the sample laminate D3 was changed to the sample laminate E3, thereby obtaining a test substrate E4.

[0624] (3. Measurement of optical transmission loss (dB / cm) of optical waveguide before test)

[0625] The same operation as 3-1. to 3-3. of Test Example 6 was performed except that the test substrate D4 was changed to the test substrate E4, and the optical transmission loss was measured and evaluated according to the same evaluation criteria as Test Example 6.

[0626] (4. Measurement of optical transmission loss (dB / cm) of optical waveguide after reflow test)

[0627] Separately from the sample laminate E4 used in the above, a test substrate E5 was prepared in the same steps. In a reflow soldering device (HAS-6116 manufactured by ANTOM), the test substrate E5 was subjected to a heat treatment five times using a thermal history of more than 1 minute at a temperature above 260°C. The value of the transmission loss after the reflow soldering test was calculated by performing the same operations as 3-1. to 3-3. of Test Example 6 on the treated test substrate E5. Furthermore, the rate of change (%) of the calculated value of the optical transmission loss after the reflow soldering test compared to the value of the optical transmission loss before the test was calculated and evaluated using the following evaluation criteria.

[0628] Evaluation Benchmarks

[0629] “◎”: The change rate is less than 20%;

[0630] “○”: The change rate is 20% or more and less than 30%;

[0631] “△”: The change rate is greater than 30% and less than 50%;

[0632] “×”: The change rate is 50% or more.

[0633] (5. Confirmation of the mode)

[0634] The same operation as in Test Example 7 was performed on the test substrate E4, and the pattern was confirmed based on the same evaluation criteria as in Test Example 7.

[0635] <Examples II-2 to II-6 and Comparative Example I-1: Formation of Optical Waveguide>

[0636] As shown in Table 4, an optical waveguide was formed in the same manner as in Example II-1 except that the combination of the core resin composition and the cladding resin composition was changed, and evaluation was performed by various tests.

[0637] The combinations of the core resin composition and the covering resin composition used in the respective Examples and Comparative Examples and the evaluation results are shown in the following Table 4. In Table 4, the abbreviations have the following meanings.

[0638] NA: Numerical aperture of the optical waveguide (the numerical aperture NA is a value expressed by the following formula (1))

[0639]

[0640] "S" in the Mode column: Single mode

[0641] "M" in the Mode column: Multimode

[0642] [Table 4]

[0643]

[0644] Marking Description

[0645] 10. Optical waveguide;

[0646] 100 core layer;

[0647] 110 second composition layer;

[0648] 111 Exposure Department;

[0649] 112 Non-exposure Department;

[0650] 200 cladding;

[0651] 210 first composition layer;

[0652] 220 Curing the first composition layer (lower coating layer);

[0653] 230 third composition layer;

[0654] 240 Cured third composition layer (upper covering layer);

[0655] 300 substrate;

[0656] 400 Mask;

[0657] 410 light-transmitting part;

[0658] 420 Shade;

[0659] 500 conductor layers.

Claims

1. A photosensitive resin composition kit comprising a core resin composition and a coating resin composition, The core resin composition and the covering resin composition respectively contain: (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group; (B) Epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, At least the coating resin composition further comprises: (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship: 0.6≤(E)clad-(E)core≤10.

2. The photosensitive resin composition kit according to claim 1, wherein: The resin (a1) contains at least one of an aralkyl type resin and a Cardo type resin.

3. The photosensitive resin composition kit according to claim 1, wherein: The resin (a2) contains a (meth)acryloyl group.

4. The photosensitive resin composition kit according to claim 1, wherein: (E) clad is 1 to 12% by mass.

5. The photosensitive resin composition kit according to claim 1, wherein: When the content of the component (C) in the core resin composition when the non-volatile component of the core resin composition is 100% by mass is denoted as (C)core, and the content of the component (C) in the coating resin composition when the non-volatile component of the coating resin composition is 100% by mass is denoted as (C)clad, (C)core and (C)clad satisfy the following relationship: 0.9≤(C)clad / (C)core≤1.

5.

6. The photosensitive resin composition kit according to claim 1, wherein: When the contents of the component (A) and the component (B) in the core resin composition when the nonvolatile component of the core resin composition is 100% by mass are represented by (A) core and (B) core, respectively, (A) core and (B) core satisfy the following relationship: 0.1≤(A)core / (B)core≤5.

7. The photosensitive resin composition kit according to claim 1, wherein: When the contents of the component (A) and the component (B) in the coating resin composition when the nonvolatile component of the coating resin composition is 100% by mass are respectively represented by (A)clad and (B)clad, (A)clad and (B)clad satisfy the following relationship: 0.1≤(A)clad / (B)clad≤5.

8. The photosensitive resin composition kit according to claim 1, wherein: When the contents of the component (A) and the component (C) in the core resin composition when the nonvolatile component of the core resin composition is 100% by mass are represented by (A)core and (C)core, respectively, (A)core and (C)core satisfy the following relationship: 0.1≤(A)core / (C)core≤5.

9. The photosensitive resin composition kit according to claim 1, wherein: When the contents of the component (A) and the component (C) in the coating resin composition when the nonvolatile component of the coating resin composition is 100% by mass are respectively represented by (A)clad and (C)clad, (A)clad and (C)clad satisfy the following relationship: 0.1≤(A)clad / (C)clad≤5.

10. The photosensitive resin composition kit according to claim 1, wherein: The core resin composition and the covering resin composition each further contain (H) an organic solvent.

11. The photosensitive resin composition kit according to claim 1, which is a photosensitive resin composition kit for producing an optical waveguide.

12. The photosensitive resin composition kit according to claim 1, which is a photosensitive resin composition kit for producing an optical waveguide capable of transmitting light having a wavelength of 1300 nm to 1320 nm.

13. The photosensitive resin composition kit according to claim 1, which is a photosensitive resin composition kit for producing a single-mode optical waveguide.

14. A photosensitive resin sheet set comprising a core resin sheet and a covering resin sheet, The core resin sheet comprises: a resin composition layer comprising the core resin composition in the photosensitive resin composition kit according to any one of claims 1 to 13; The coating resin sheet comprises a resin composition layer containing the coating resin composition in the photosensitive resin composition kit according to any one of claims 1 to 13.

15. A photosensitive resin ink set comprising a core resin ink and a coating resin ink, The core resin ink comprises: the core resin composition in the photosensitive resin composition kit according to any one of claims 1 to 13, The coating resin ink comprises the coating resin composition in the photosensitive resin composition kit according to any one of claims 1 to 13.

16. An optical waveguide comprising a core layer and a cladding layer, The core layer comprises a cured product of a core resin composition, wherein the core resin composition comprises: (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group; (B) Epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, May also include: (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, The coating layer comprises a cured product of a coating resin composition, wherein the coating resin composition comprises: (A) a carboxyl group-containing resin (a1) or a resin (a2) containing an epoxy group and a free radical polymerizable group; (B) Epoxy resin; (C) a photocurable resin; (D) a photopolymerization initiator; and (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship: 0.6≤(E)clad-(E)core≤10.

17. An optoelectronic hybrid substrate comprising the optical waveguide according to claim 16.

18. A method for manufacturing an optical waveguide, comprising the following steps in sequence: A step of forming a first composition layer including a coating resin composition; a step of curing the first composition layer; forming a second composition layer including a core resin composition on the first composition layer; A step of subjecting the second composition layer to an exposure treatment; A step of developing the second composition layer; a step of curing the second composition layer; forming a third composition layer including a coating resin composition on the second composition layer; and a step of curing the third composition layer, The core resin composition and the covering resin composition respectively contain: (A) a carboxyl group-containing resin (a1); (B) Epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, At least the coating resin composition further comprises: (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship: 0.6≤(E)clad-(E)core≤10.

19. A method for manufacturing an optical waveguide, comprising the following steps in sequence: A step of forming a first composition layer including a coating resin composition; a step of curing the first composition layer; forming a second composition layer including a core resin composition on the first composition layer; a step of curing the second composition layer; forming a fourth composition layer including a resist composition on the second composition layer; A step of subjecting the fourth composition layer to an exposure treatment; A step of developing the fourth composition layer; forming a pattern on the second composition layer; forming a third composition layer including a coating resin composition on the second composition layer; and a step of curing the third composition layer, The core resin composition and the covering resin composition respectively contain: (A) a resin (a2) containing an epoxy group and a free radical polymerizable group; (B) Epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, At least the coating resin composition further comprises: (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship: 0.6≤(E)clad-(E)core≤10.

20. A method for manufacturing an optoelectronic hybrid substrate, which comprises the following steps in sequence: A step of forming a first composition layer including a coating resin composition; a step of curing the first composition layer; forming a second composition layer including a core resin composition on the first composition layer; A step of subjecting the second composition layer to an exposure treatment; A step of developing the second composition layer; a step of curing the second composition layer; forming a third composition layer including a coating resin composition on the second composition layer; and a step of curing the third composition layer, The core resin composition and the covering resin composition respectively contain: (A) a carboxyl group-containing resin (a1); (B) Epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, At least the coating resin composition further comprises: (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship: 0.6≤(E)clad-(E)core≤10.

21. A method for manufacturing an optoelectronic hybrid substrate, which comprises the following steps in sequence: A step of forming a first composition layer including a coating resin composition; a step of curing the first composition layer; forming a second composition layer including a core resin composition on the first composition layer; a step of curing the second composition layer; forming a fourth composition layer including a resist composition on the second composition layer; A step of subjecting the fourth composition layer to an exposure treatment; A step of developing the fourth composition layer; forming a pattern on the second composition layer; forming a third composition layer including a coating resin composition on the second composition layer; and a step of curing the third composition layer, The core resin composition and the covering resin composition respectively contain: (A) a resin (a2) containing an epoxy group and a free radical polymerizable group; (B) Epoxy resin; (C) a photocurable resin; and (D) a photopolymerization initiator, At least the coating resin composition further comprises: (E) an alkoxysilane compound having one or more functional groups selected from the group consisting of an epoxy group, a phenylamino group, a vinyl group and a (meth)acryloyl group, When the content (mass %) of the component (E) in the core resin composition when the non-volatile component of the core resin composition is 100 mass % is denoted as (E)core, and the content (mass %) of the component (E) in the coating resin composition when the non-volatile component of the coating resin composition is 100 mass % is denoted as (E)clad, (E)core and (E)clad satisfy the following relationship: 0.6≤(E)clad-(E)core≤10.

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