CN117991587A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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CN117991587A
CN117991587A CN202311407587.3A CN202311407587A CN117991587A CN 117991587 A CN117991587 A CN 117991587A CN 202311407587 A CN202311407587 A CN 202311407587A CN 117991587 A CN117991587 A CN 117991587A
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resin composition
photosensitive resin
layer
less
optical waveguide
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入泽真治
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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  • Optical Integrated Circuits (AREA)
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Abstract

The invention provides a photosensitive resin composition which can manufacture optical waveguides with excellent plating adhesion, excellent core forming property and small transmission loss. The solution of the present invention is a photosensitive resin composition comprising: an epoxy resin (A), a resin (B) containing a carboxyl group and an olefinic double bond, a photopolymerization initiator (C), and a non-developable polymer having a solubility parameter (SP value) of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less).

Description

Photosensitive resin composition
Technical Field
The invention relates to a photosensitive resin composition, a resin sheet, a photosensitive resin composition set, an optical waveguide, a method for manufacturing the optical waveguide, and an opto-electric hybrid board.
Background
The demands for ultra-high speed and large capacity of communication are increasing due to the progress of technologies such as 5G communication, autopilot, ioT, artificial intelligence, and big data. The semiconductor package supporting the base thereof has conventionally been adapted to cope with high-speed communication by passing a high-frequency current. However, in recent years, problems of noise generation, communication loss, and heat release caused by high-speed communication have become more and more remarkable. In order to solve these problems, in recent years, the power wiring board is actively equipped with an optical circuit to achieve energy saving, low delay and high-speed communication (patent documents 1 and 2).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2019-211540
Patent document 2: japanese patent No. 5771978.
Disclosure of Invention
Problems to be solved by the invention
Particularly in data centers requiring high-speed transmission, studies related to the introduction of silicon photoelectrons (Silicon Photonics) are actively conducted. The silicon photoelectrons have high matching with the conventional LSI manufacturing process. Therefore, by using silicon photoelectrons, it is expected that a thin line waveguide of a nanometer size can be formed at low cost according to a technology developed in an electronic circuit integration technology.
For example, silicon optoelectronics can be expected to form an optical integrated circuit on a chip using a thin line waveguide. In the case of manufacturing an opto-electronic hybrid board on which the chip is mounted, it is necessary to provide an optical waveguide on the opto-electronic hybrid board in order to take out signal light from a thin line waveguide in the chip to the outside of the chip and to connect the signal light to wiring between the chips. From the viewpoint of efficiently forming a fine optical waveguide, it is desirable to form the optical waveguide from a cured product of the photosensitive resin composition. Therefore, excellent core formability is desired for forming a fine core layer. In addition, in order to suppress attenuation of the signal light, it is also desirable to suppress transmission loss of the optical waveguide.
In recent years, it is also conceivable to provide a conductor layer by performing a metal plating treatment on the core layer of the optical waveguide. In order to improve the adhesion between the core layer and the conductor layer, a method of roughening the surface of the core layer to provide irregularities is considered, but if the surface of the core layer is provided with irregularities, the transmission loss of the optical waveguide may be reduced, and the function as the optical waveguide may be lost.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive resin composition capable of producing an optical waveguide having excellent plating adhesion, excellent core formability, and small transmission loss; a resin sheet containing the photosensitive resin composition; a photosensitive resin composition set; an optical waveguide; an opto-electronic hybrid board.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems. As a result, the present inventors found that: the present invention has been completed by using a photosensitive resin composition comprising a combination of (a) an epoxy resin, (B) a resin containing a carboxyl group and an olefinic double bond, (C) a photopolymerization initiator, and (D) a non-developable polymer having a solubility parameter (SP value) of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less), and thereby producing an optical waveguide excellent in plating adhesion, excellent in core formability, and small in transmission loss.
That is, the present invention includes the following aspects;
[1] A photosensitive resin composition comprising:
(A) An epoxy resin,
(B) A resin containing carboxyl groups and olefinic double bonds,
(C) Photopolymerization initiator
(D) A non-developable polymer having a solubility parameter (SP value) of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less;
[2] the photosensitive resin composition according to [1], wherein the weight average molecular weight of the component (D) is 3000 or more and 100000 or less;
[3] The photosensitive resin composition according to [1] or [2], wherein the component (D) comprises an acrylic polymer;
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (D) has a structural unit represented by the following formula (D-1) and a structural unit represented by the following formula (D-2),
[ Chemical formula 1]
In the formula (D-1), R 1 independently represents a hydrogen atom or a methyl group, R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, p independently represents an integer of 2 to 4, q represents an integer of 2 to 100,
In the formula (D-2), R 3 independently represents a hydrogen atom or a methyl group, and R 4 independently represents an alkyl group having 1 to 22 carbon atoms;
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the solubility parameter (SP value) of the component (B) is 9 (cal/cm 3)1/2 or more and 11 (cal/cm 3)1/2 or less;
[6] The photosensitive resin composition according to any one of [1] to [5], further comprising (E) an inorganic filler having an average particle diameter of 100nm or less;
[7] The photosensitive resin composition according to any one of [1] to [6], which is used for producing a core layer of an optical waveguide;
[8] a resin sheet comprising a support and a photosensitive resin composition layer formed on the support,
The photosensitive resin composition layer comprising the photosensitive resin composition of any one of [1] to [7 ];
[9] The resin sheet according to [8], wherein the photosensitive resin composition layer has a thickness of 1 μm or more and 15 μm or less;
[10] A photosensitive resin composition set comprising a photosensitive resin composition for cores and a resin composition for coating,
The photosensitive resin composition for a core comprising the photosensitive resin composition of any one of [1] to [7 ];
[11] An optical waveguide having a core layer and a cladding layer,
The core layer comprising a cured product of the photosensitive resin composition according to any one of [1] to [7 ];
[12] The optical waveguide of [11] capable of transmitting light having a wavelength of 1300nm to 1320 nm;
[13] the optical waveguide of [12], which is a single-mode optical waveguide;
[14] An opto-electric hybrid board comprising the optical waveguide described in [11] to [13 ].
Effects of the invention
According to the present invention, a photosensitive resin composition capable of producing an optical waveguide having excellent plating adhesion, excellent core formability, and small light transmission loss can be provided; a photosensitive resin composition set containing the photosensitive resin composition; an optical waveguide; an opto-electronic hybrid board.
Drawings
FIG. 1 is a perspective view schematically showing an optical waveguide of one embodiment of the present invention;
Fig. 2 is a schematic cross-sectional view illustrating a process (I) of a method for manufacturing an optical waveguide according to an embodiment of the present invention;
fig. 3 is a schematic cross-sectional view of step (II) for explaining a method of manufacturing an optical waveguide according to an embodiment of the present invention;
fig. 4 is a schematic cross-sectional view illustrating a step (III) of a method for manufacturing an optical waveguide according to an embodiment of the present invention;
fig. 5 is a schematic cross-sectional view of a step (IV) for explaining a method for manufacturing an optical waveguide according to an embodiment of the present invention;
Fig. 6 is a schematic cross-sectional view illustrating a process (V) of a method for manufacturing an optical waveguide according to an embodiment of the present invention;
fig. 7 is a schematic cross-sectional view illustrating a step (VI) of a method for manufacturing an optical waveguide according to an embodiment of the present invention;
Fig. 8 is a schematic cross-sectional view illustrating a step (VII) of a method for manufacturing an optical waveguide according to an embodiment of the present invention;
fig. 9 is a schematic cross-sectional view illustrating a step (VIII) of a method for manufacturing an optical waveguide according to an embodiment of the present invention;
Fig. 10 is a schematic cross-sectional view illustrating a process (IX) of a method for manufacturing an optical waveguide according to an embodiment of the present invention.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented with any modification within the scope of the claims and their equivalents.
[ Photosensitive resin composition ]
The photosensitive resin composition of the present invention comprises (A) an epoxy resin, (B) a resin containing a carboxyl group and an olefinic double bond, (C) a photopolymerization initiator, and (D) a non-developable polymer having a solubility parameter (SP value) of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less).
The photosensitive resin composition of the present invention may further contain any component in combination with the components (a) to (D). Examples of the optional component include: (E) An inorganic filler having an average particle diameter of 100nm or less, (F) a reactive diluent, (G) a solvent, and (H) other additives. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.
In the following description, the term "(meth) acrylic" includes acrylic acid, methacrylic acid, and combinations thereof, and the term "(meth) acrylate" includes acrylate, methacrylate, and combinations thereof, unless otherwise specified.
In the present invention, the content of each component in the photosensitive resin composition is a value obtained when the nonvolatile component in the photosensitive resin composition is 100 mass%, unless otherwise explicitly stated.
Epoxy resin (A)
The photosensitive resin composition contains an epoxy resin (a) as a component (a). (A) The epoxy resin is a curable resin having an epoxy group.
Examples of the epoxy resin (a) include: a bisxylenol (bixylenol) epoxy resin; bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, and other bisphenol type epoxy resins; dicyclopentadiene type epoxy resins; novolac type epoxy resins such as triphenol type epoxy resins and phenol novolac type epoxy resins; t-butyl-catechol epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthalene type epoxy resins, naphthol aralkyl type epoxy resins, naphthalene ether type epoxy resins, and naphthol novolac type epoxy resins; an anthracene-type epoxy resin; glycidol amine type epoxy resin; glycidyl ester type epoxy resins; cresol novolac type epoxy resin; phenol aralkyl type epoxy resin; an epoxy resin containing a biphenyl skeleton; linear aliphatic epoxy resin; an epoxy resin having a butadiene structure; a cycloaliphatic epoxy resin; a heterocyclic epoxy resin; epoxy resins containing spiro rings; cyclohexane type epoxy resin; cyclohexane dimethanol type epoxy resin; a trimethylol type epoxy resin; tetraphenylethane type epoxy resin; isocyanurate type epoxy resins; phenol benzopyrrolidone (phenolphthalimidine) type epoxy resins, and the like. Among them, from the viewpoint of remarkably obtaining the effect of the present invention, the (a) epoxy resin preferably contains any one of naphthalene type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl skeleton-containing epoxy resin, and bisphenol a type epoxy resin. (A) The epoxy resin may be used alone or in combination of 1 or more than 2.
The photosensitive resin composition of the present invention preferably contains (a) an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the (a) epoxy resin.
(A) The epoxy resin includes an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin") and an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin"). In the photosensitive resin composition of the present invention, the epoxy resin (a) may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin, and particularly preferably contains only a solid epoxy resin.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
The solid epoxy resin is preferably any one of a binaphthol epoxy resin, a naphthalene tetrafunctional epoxy resin, a naphthol novolac epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a triphenol epoxy resin, a naphthol epoxy resin, a biphenyl epoxy resin, a naphthalene ether epoxy resin, an anthracene epoxy resin, a bisphenol a epoxy resin, a bisphenol AF epoxy resin, a phenol aralkyl epoxy resin, a tetraphenyl ethane epoxy resin, and a phenol benzopyrrolone epoxy resin, more preferably a naphthalene epoxy resin, a naphthol epoxy resin, and a biphenyl epoxy resin, and further preferably a naphthalene epoxy resin.
Specific examples of the solid epoxy resin include: "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Co; "HP-4700", "HP-4710" manufactured by DIC corporation (naphthalene type tetrafunctional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" manufactured by DIC Co., ltd. (cresol novolak type epoxy resin); "N-673" manufactured by DIC corporation (cresol novolac type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" manufactured by DIC; "EPPN-502H" (triphenol epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical pharmaceutical company; "ESN475V" and "ESN4100V" manufactured by Nissan chemical materials Co., ltd. (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "ESN375" manufactured by Nissan chemical materials Co., ltd. (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "YX7700" manufactured by Mitsubishi chemical corporation (phenol aralkyl type epoxy resin); "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd. The number of these may be 1 alone or 2 or more.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.
As the liquid epoxy resin, glycirol 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 are preferable.
Specific examples of the liquid epoxy resin include: "EX-992L" manufactured by Nagase ChemteX, YX7400 "manufactured by Mitsubishi chemical corporation, and" HP4032 "manufactured by DIC, HP4032D, HP4032SS" (naphthalene type epoxy resin); "828US", "jER828EL", "825", "Epikote 828EL" manufactured by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (Glycirol type epoxy resin) manufactured by ADEKA Co; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Co; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co., ltd; "ZX1059" manufactured by Nissan chemical materials Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "EX-991L" (epoxy resin having an alkylene oxide skeleton and a butadiene skeleton) manufactured by Nagase ChemteX Co., ltd; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by macrocellulite corporation; "PB-3600" by Daxillon corporation, and "JP-100" and "JP-200" by Japan, respectively (epoxy resin having butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "EG-280" manufactured by Osaka gas chemical Co., ltd. (epoxy resin containing fluorene structure); "EX-201" (Cyclic aliphatic glycidyl Ether) manufactured by Nagase ChemteX Co.
As the (a) epoxy resin, in the case of using a solid epoxy resin and a liquid epoxy resin in combination, the mass ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, particularly preferably 2:1 to 1:10.
(A) The epoxy resin preferably contains an epoxy resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton, and particularly preferably contains an epoxy resin having a naphthalene skeleton.
(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 2,000g/eq, still more preferably 70g/eq to 1,000g/eq, still more preferably 80g/eq to 500g/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.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
When the nonvolatile content of the photosensitive resin composition is set to 100% by mass, the content of the (a) epoxy resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, from the viewpoint of remarkably obtaining the effect of the present invention.
(B) resins containing carboxyl groups and olefinic double bonds ]
In the photosensitive resin composition of the present invention, the component (B) contains a resin containing a carboxyl group and an olefinic double bond, and the component (A) is excluded from the resins. (B) The components may be used alone or in combination of 1 or more than 2.
(B) Since the resin containing a carboxyl group and an olefinic double bond contains a carboxyl group as an acidic group, the photosensitive resin composition of the present invention can exhibit solubility in an alkaline developer such as a1 mass% aqueous sodium carbonate solution. In the resin (B) containing a carboxyl group and an olefinic double bond, the number of carboxyl groups in 1 molecule may be 1 or 2 or more.
(B) The resin containing a carboxyl group and an olefinic double bond contains an olefinic double bond as an aliphatic carbon-carbon unsaturated bond. Therefore, (B) the resin containing a carboxyl group and an olefinic double bond can be polymerized in the case where (C) the photopolymerization initiator generates a radical.
(B) Resins containing carboxyl groups and olefinic double bonds generally have the aforementioned groups containing olefinic double bonds. This group is generally radically polymerizable, and therefore, may be referred to as "radically polymerizable group" hereinafter. Examples of the radical polymerizable group include a (meth) acryloyl group (acryl or methacryl), vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadic imide group, and the like, and from the viewpoint of reactivity in radical polymerization, a (meth) acryloyl group is preferable.
The number of radical polymerizable groups in the resin containing a carboxyl group and an olefinic double bond per 1 molecule (B) may be 1 or 2 or more.
In one embodiment, (B) the resin containing carboxyl groups and olefinic double bonds is preferably an acid modified epoxy (meth) acrylate resin.
The acid-modified epoxy (meth) acrylate resin has a (meth) acryl group, and thus, in one embodiment, photo radical polymerization can occur. The number of (meth) acryloyl groups in each 1 molecule of the acid-modified epoxy (meth) acrylate resin may be 1 or 2 or more.
The acid-modified epoxy (meth) acrylate resin is preferably a resin having both a (meth) acryloyl group and a carboxyl group, capable of undergoing photo radical polymerization and capable of undergoing alkali development.
The acid-modified epoxy (meth) acrylate resin can be produced by acid-modifying an epoxy (meth) acrylate resin by a known method. The epoxy (meth) acrylate resin can be produced, for example, by reacting an epoxy resin with acrylic acid or methacrylic acid.
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 a molecule. Examples thereof include: bisphenol type epoxy resins such as bisphenol type a epoxy resins, hydrogenated bisphenol type a epoxy resins, bisphenol type F epoxy resins, hydrogenated bisphenol type F epoxy resins, bisphenol type S epoxy resins, and modified bisphenol type F epoxy resins obtained by reacting bisphenol type F epoxy resins with epichlorohydrin to modify the epoxy resins to have three or more functions; biphenol type epoxy resins, tetramethyl biphenol type epoxy resins and the like; phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a type novolac type epoxy resins, alkylphenol novolac type epoxy resins, and other novolac type epoxy resins; fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; naphthalene type epoxy resins (naphthalene skeleton-containing epoxy resins) having a naphthalene skeleton such as naphthalene type epoxy resins, dihydroxynaphthalene type epoxy resins, polyhydroxy binaphthyl type epoxy resins, naphthol aralkyl type epoxy resins, binaphthol type epoxy resins, naphthalene ether type epoxy resins, naphthol novolac type epoxy resins, naphthalene type epoxy resins obtained by condensation reaction of polyhydroxy naphthalene with aldehydes, and the like; a bisxylenol type epoxy resin; dicyclopentadiene type epoxy resins; a triphenol type epoxy resin; t-butyl-catechol epoxy resin; an epoxy resin having a condensed ring skeleton such as an anthracene-type epoxy resin; glycidol amine type epoxy resin; glycidyl ester type epoxy resins; biphenyl type epoxy resin; linear aliphatic epoxy resin; an epoxy resin having a butadiene structure; a cycloaliphatic epoxy resin; a heterocyclic epoxy resin; epoxy resins containing spiro rings; cyclohexane dimethanol type epoxy resin; a trimethylol type epoxy resin; tetraphenylethane type epoxy resin; glycidyl group-containing acrylic resins such as polyglycidyl (meth) acrylate and copolymers of glycidyl methacrylate and acrylate; fluorene type epoxy resins; halogenated epoxy resins, and the like.
From the viewpoint of remarkably obtaining the effect of the present invention, the epoxy resin used for producing the epoxy (meth) acrylate resin is preferably an epoxy resin containing an aromatic skeleton. Here, the aromatic skeleton is a concept including polycyclic aromatic and aromatic heterocyclic rings as well. Among them, any one of cresol novolac type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin and naphthol aralkyl type epoxy resin is preferable, and naphthol aralkyl type epoxy resin is more preferable.
In one embodiment, the acid-modified epoxy (meth) acrylate resin preferably includes an acid-modified epoxy (meth) acrylate resin having a skeleton selected from the group consisting of a naphthol aralkyl skeleton, a naphthalene skeleton, and a biphenyl skeleton, and particularly preferably includes an acid-modified epoxy (meth) acrylate resin having a naphthol aralkyl skeleton.
In one embodiment, the acid-modified epoxy (meth) acrylate resin preferably includes a resin selected from acid-modified epoxy (meth) acrylate resins (hereinafter referred to as "ester-type acid-modified epoxy (meth) acrylate resins") obtained by esterifying hydroxyl groups of the epoxy (meth) acrylate resins and acid-modified epoxy (meth) acrylate resins (hereinafter referred to as "urethane-type acid-modified epoxy (meth) acrylate resins") obtained by urethanizing hydroxyl groups of the epoxy (meth) acrylate resins, and particularly preferably includes an ester-type acid-modified epoxy (meth) acrylate resin.
The ester acid-modified epoxy (meth) acrylate resin can be produced, for example, by reacting an epoxy (meth) acrylate resin with a polycarboxylic anhydride. The ester acid-modified epoxy (meth) acrylate resin may be used alone or in combination of 1 or more than 2.
Examples of the polycarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic dianhydride, and any of these may be used alone or in combination of two or more. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferable, and tetrahydrophthalic anhydride is more preferable.
The ester-type acid-modified epoxy (meth) acrylate resin preferably contains a resin selected from the group consisting of an ester-type acid-modified epoxy (meth) acrylate resin containing a cresol novolac skeleton, an ester-type acid-modified epoxy (meth) acrylate resin containing a bisphenol a skeleton, an ester-type acid-modified epoxy (meth) acrylate resin containing a bisphenol F skeleton, an ester-type acid-modified epoxy (meth) acrylate resin containing a biphenyl skeleton, and an ester-type acid-modified epoxy (meth) acrylate resin containing a naphthol aralkyl skeleton.
The ester-type acid-modified epoxy (meth) acrylate resin can be synthesized by a known method, and commercially available ones can be used. Specific examples of the commercial products include: "CCR-1373H" (acid-modified epoxy acrylate resin containing a cresol novolak skeleton), "ZCR-8001H" (acid-modified epoxy acrylate resin containing a bisphenol skeleton), "ZCR-1569H" (acid-modified epoxy acrylate resin containing a biphenyl skeleton), "CCR-1171H" (acid-modified epoxy acrylate resin containing a cresol novolak skeleton), "ZCR-1797H", ZCR-1761H "(acid-modified epoxy acrylate resin containing a biphenyl skeleton)," ZAR-2000 "(acid-modified epoxy acrylate resin containing a bisphenol A skeleton), and" ZFR-1491H ", ZFR-1533H" (acid-modified epoxy acrylate resin containing a bisphenol F skeleton), and "PR-300CP" (acid-modified epoxy acrylate resin containing a cresol novolak skeleton) and "CCR-1179" (epoxy acrylate resin containing a cresol novolak skeleton) made by Japanese chemical company.
The urethane-type 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-type acid-modified epoxy (meth) acrylate resin may be used alone or in combination of 1 or more than 2.
Examples of the diisocyanate compound include: aromatic diisocyanate compounds such as xylylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (xylylene diisocyanate), tetramethylxylylene diisocyanate, diphenyl diisocyanate, and naphthalene diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, propine sulfone ether diisocyanate, ethyl methyl ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethyl hexamethylene diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane.
Examples of the diol compound having a carboxyl group include dimethylolpropionic acid, dimethylolbutyric acid, and dimethylolnonanoic acid.
The urethane-type acid-modified epoxy (meth) acrylate resin preferably contains a resin selected from the group consisting of a urethane-type acid-modified epoxy (meth) acrylate resin containing a cresol novolac skeleton, a urethane-type acid-modified epoxy (meth) acrylate resin containing a bisphenol a skeleton, a urethane-type acid-modified epoxy (meth) acrylate resin containing a bisphenol F skeleton, a urethane-type acid-modified epoxy (meth) acrylate resin containing a biphenyl skeleton, and a urethane-type acid-modified epoxy (meth) acrylate resin containing a naphthol aralkyl skeleton.
The urethane-type acid-modified epoxy (meth) acrylate resin may be synthesized by a known synthesis method, or may be commercially available. As a known synthesis method, for example, a method described in Japanese patent application laid-open No. 2016-199719 is mentioned. Specific examples of the commercial products include "UXE-3024", "UXE-3011", "UXE-3012", "UXE-3024" manufactured by Nippon Kagaku Co., ltd.
The acid value of the component (B) is preferably 0.1mgKOH/g or more, more preferably 0.5mgKOH/g or more, still more preferably 1mgKOH/g or more, 10mgKOH/g or more, still more preferably 20mgKOH/g or more, 30mgKOH/g or more, particularly preferably 40mgKOH/g or more, 50mgKOH/g or more, from the viewpoint of improving the alkali developability of the photosensitive resin composition. (B) The upper limit of the acid value of the component is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 120mgKOH/g or less, particularly preferably 100mgKOH/g or less.
(B) The weight average molecular weight of the component (a) is preferably 20000 or less, more preferably 17000 or less, still more preferably 15000 or less, preferably 500 or more, more preferably 750 or more, still more preferably 900 or more. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by Gel Permeation Chromatography (GPC).
In the component (B), the solubility parameter (SP value) of the component (B) is preferably a value close to the SP value of the component (D) from the viewpoint of improving the compatibility with the component (D) described later. (B) The SP value of the component is preferably 9 (cal/cm 3)1/2 or more, more preferably 9.5 (cal/cm 3)1/2 or more, preferably 11 (cal/cm 3)1/2 or less, more preferably 10.5 (cal/cm 3)1/2 or less.) the SP value can be calculated using Fedors theory.
When the nonvolatile content of the photosensitive resin composition is set to 100% by mass, the content of the component (B) is preferably 15% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, preferably 55% by mass or less, further preferably 50% by mass or less, and particularly preferably 45% by mass or less, from the viewpoint of improving the alkali developability.
(B) The mass ratio of the component (a) to the epoxy resin (the mass (mass%) of the component (B) when the nonvolatile component of the photosensitive resin composition is 100 mass%)/the mass (mass%) of the component (a) when the nonvolatile component of the photosensitive resin composition is 100 mass%) is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
(C) photopolymerization initiator ]
The photosensitive resin composition of the present invention contains a photopolymerization initiator (C) as a component (C). (C) Photopolymerization initiators are generally capable of receiving light to generate free radicals. The photopolymerization initiator (C) as the component (C) does not include any substances belonging to the components (A) and (B). (C) The components may be used alone or in combination of 1 or more than 2.
As the component (C), a photopolymerization initiator capable of effectively photocuring the photosensitive resin composition can be used. As such a photopolymerization initiator, it is preferable to include any one of (C1) a photopolymerization initiator having a molecular weight of 420 or more and (C2) a photopolymerization initiator having a molecular weight of less than 420. (C1) The component (C) and the component (C2) may be used in combination, but from the viewpoint of significantly obtaining the effect of the present invention, the component (C) preferably contains any one of the component (C1) and the component (C2), and more preferably contains the component (C2).
A photopolymerization initiator having a molecular weight of 420 or more (C1)
The molecular weight of the component (C1) is usually 420 or more, preferably 500 or more, more preferably 600 or more and 700 or more, from the viewpoint of enabling formation of fine wiring and production of an optical waveguide having a small optical transmission loss. The upper limit is not particularly limited, but is preferably 3000 or less, more preferably 2500 or less, and still more preferably 2000 or less.
As the component (C1), a compound having a molecular weight of 420 or more, having a group that absorbs active light such as ultraviolet rays, and capable of efficiently performing photopolymerization can be used. As the component (C1), for example, a compound containing a structural unit represented by the formula (C-1) is preferable,
[ Chemical formula 2]
(Wherein R 1 represents an active light-absorbing group; R 2 each independently represents a divalent hydrocarbon group; n represents an integer of 1 to 10; a bond is represented).
R 1 represents an active light absorbing group. The active light absorbing group is a group capable of absorbing active light such as ultraviolet rays. Examples of the active light absorbing group include a group having an aminoketone skeleton, a group having an anthraquinone skeleton, a group having a thioxanthone skeleton, a group having a ketal skeleton, a group having a benzophenone skeleton, a group having a xanthone skeleton, a group having an acetophenone skeleton, a group having a benzoin skeleton, a group having a thioxanthone skeleton, a group having a benzoate skeleton, and the like, as long as the active light absorbing group is a functional group capable of absorbing active light.
Specific examples of the active light absorbing group include the following groups (i) to (vii). Among them, any one of (i) and (ii) is preferable as the active light absorbing group. Wherein, represents a bond;
[ chemical formula 3]
R 2 each independently represents a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, and from the viewpoint of significantly obtaining the effect of the present invention, a divalent aliphatic hydrocarbon group is preferable.
The divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group, and examples thereof include an alkylene group and an alkenylene group, and more preferably an alkylene group. The alkylene group may be any of linear, branched, and cyclic, and is preferably linear. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 3 carbon atoms. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and cyclohexylene, and methylene is preferred. The alkenylene group may be any of linear, branched, and cyclic, and is preferably linear. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms.
Examples of the divalent aromatic hydrocarbon group include arylene and heteroarylene. The arylene group and the heteroarylene group are preferably arylene groups or heteroarylene groups having 6 to 20 carbon atoms, and more preferably arylene groups or heteroarylene groups having 6 to 10 carbon atoms.
The divalent hydrocarbon group may optionally have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group.
N represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.
(C1) The component (C-3) preferably contains a compound represented by the following general formula (C-2) or a compound represented by the following general formula (C-3):
[ chemical formula 4]
(In the general formula (C-2), R 11 each independently represents an active light-absorbing group; R 12 each independently represents a divalent hydrocarbon group; R 13 represents an m-valent hydrocarbon group; n1 represents an integer of 1 to 10; m represents an integer of 1 to 4;
In the general formula (C-3), R 21、R23 each independently represents an active light-absorbing group; r 22 each independently represents a divalent hydrocarbon group. n2 represents an integer of 1 to 10. ).
R 11 each independently represents an active light-absorbing group, which is the same as the active light-absorbing group represented by R 1 in formula (C-1).
R 12 each independently represents a divalent hydrocarbon group, which is the same as the divalent hydrocarbon group represented by R 2 in the formula (C-1).
R 13 represents an m-valent hydrocarbon group. Examples of the m-valent hydrocarbon group include an m-valent aliphatic hydrocarbon group and an m-valent aromatic hydrocarbon group, and an m-valent aliphatic hydrocarbon group is preferable, and for example, when m is 3, a trivalent group obtained by removing 3 hydrogen atoms from an alkane is preferable. Specific examples of the group represented by R 13 include the following groups. Wherein "+" represents a bond;
[ chemical formula 5]
。
N1 represents an integer of 1 to 10, and is the same as n in formula (C-1).
M represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 3.
R 21 and R 23 each independently represent an active light-absorbing group, which is the same as the active light-absorbing group represented by R 1 in the formula (C-1).
R 22 each independently represents a divalent hydrocarbon group, which is the same as the divalent hydrocarbon group represented by R 2 in the formula (C-1).
Specific examples of the component (C1) include the following compounds. The component (C1) is not limited to these specific examples. a. b, c and d each represent an integer of 1 to 10;
[ chemical formula 6]
。
(C1) The components may be commercially available ones. Examples of the commercial products include "Omnipol910", "OmnipolTP", and "Omnipol9210" manufactured by IGM corporation.
The content of the component (C1) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, and 1 mass% or more, preferably 10 mass% or less, more preferably 8 mass% or less, and still more preferably 5 mass% or less, when the nonvolatile component of the photosensitive resin composition is 100 mass% from the viewpoint of significantly obtaining the effect of the present invention.
Photopolymerization initiators having a molecular weight of less than 420 (C2)
The molecular weight of the component (C2) is less than 420, preferably 418 or less, and more preferably 415 or less from the viewpoint of significantly obtaining the effect of the present invention. The lower limit is not particularly limited, but is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.
Examples of the component (C2) include oxime ester photopolymerization initiators, α -aminoketone photopolymerization initiators, phosphine oxide photopolymerization initiators, α -hydroxyketone photopolymerization initiators, benzoin photopolymerization initiators, benzil ketal (benzil ketal) photopolymerization initiators, and acylphosphine photopolymerization initiators.
Examples of the oxime ester photopolymerization initiator include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl ] octan-1-one (OXE 01), [1- [ 9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl ] ethylideneamino ] acetate (OXE 02), and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetoxime).
Examples of the α -aminoketone photopolymerization initiator include 2-methyl-1-phenyl-2-morpholinopropane-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-methyl-1- (4-hexylphenyl) -2-morpholinopropane-1-one, 2-ethyl-2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-methylphenylmethyl) -1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- (9, 9-dibutylfluoren-2-yl) -2-morpholinopropane-1-one, and the like.
Examples of the phosphine oxide-based photopolymerization initiator include bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, polyoxyethylene glyceryl ether tris [ phenyl (2, 4, 6-trimethylbenzoyl) phosphinate ] (Polymeric TPO-L), and the like.
Examples of the α -hydroxyketone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropion, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methylpropone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one, and the like.
Examples of the benzoin photopolymerization initiator include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of the benzil ketal photopolymerization initiator include 2, 2-dimethoxy-2-phenylacetophenone and the like.
Examples of the acylphosphine photopolymerization initiator include bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide.
In one embodiment, from the viewpoint of significantly obtaining the effect of the present invention, the (C2) component preferably contains any one of an oxime ester-based photopolymerization initiator, an α -aminoketone-based photopolymerization initiator, and an acylphosphine-based photopolymerization initiator.
(C2) The components may be commercially available ones. Specific examples of the commercial product of the component (C2) include: "Omnirad907", "Omnirad369", "Omnirad379EG", "Omnirad819", "OmniradTPO" manufactured by IGM corporation; "IrgacureTPO", "IrgacureOXE-01", "IrgacureOXE-02" by BASF corporation; "N-1919" manufactured by ADEKA, inc.
The content of the (C2) component is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, and 1 mass% or more, preferably 10 mass% or less, more preferably 8 mass% or less, and still more preferably 5 mass% or less, when the nonvolatile component of the photosensitive resin composition is 100 mass% from the viewpoint of significantly obtaining the effect of the present invention.
The content of the component (C) ((total content of the component (C1) and the component (C2)) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, and 1 mass% or more, preferably 10 mass% or less, more preferably 8 mass% or less, still more preferably 5 mass% or less, when the nonvolatile component of the photosensitive resin composition is 100 mass% from the viewpoint of significantly obtaining the effects of the present invention.
(C) The mass ratio of the component (a) to the epoxy resin (the mass (mass%) of the component (C) when the nonvolatile component of the photosensitive resin composition is 100 mass%)/the mass (mass%) of the component (a) when the nonvolatile component of the photosensitive resin composition is 100 mass%)) is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.1 or more from the viewpoint of remarkably obtaining the effect of the present invention. The upper limit is preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.3 or less.
(C) The mass ratio of the component (C) to the resin (B) containing a carboxyl group and an olefinic double bond (mass% of the component (C) when the nonvolatile component of the photosensitive resin composition is 100 mass%)/mass% of the component (B) when the nonvolatile component of the photosensitive resin composition is 100 mass%)) is preferably 0.0001 or more, more preferably 0.001 or more, and even more preferably 0.01 or more, from the viewpoint of remarkably obtaining the effect of the present invention. The upper limit is preferably 1 or less, more preferably 0.5 or less, and still more preferably 0.1 or less.
The photosensitive resin composition may contain tertiary amines such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, amyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. as a photopolymerization initiator in combination with the component (C). The photopolymerization initiator may be used alone or in combination of 1 or more than 2.
The non-developable polymer having a solubility parameter (SP value) of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less)
The non-developable polymer has a solubility parameter of 9 (cal/cm 3)1/2 to 13 (cal/cm 3)1/2), and is a polymer having a solubility parameter of 9 (cal/cm 3)1/2 to 13 (cal/cm 3)1/2) and having a solubility in a developer lower than that of the components (A) and (B), and the component (D) is usually compatible with the components (A) and (B) at a high compatibility, and further has a high solubility in a chemical solution used for roughening treatment, and the component (D) has a SP value of 9 (cal/cm 3)1/2 to 13 (cal/cm 3)1/2) and is not included in the non-developable polymer, but the components (D) belonging to the components (A) to (C) may be used alone or in combination of 1 or 2 or more.
The SP value of the component (D) is 9 (cal/cm 3)1/2 or more, preferably 9.1 (cal/cm 3)1/2 or more, more preferably 9.2 (cal/cm 3)1/2 or more) from the viewpoint of obtaining a cured product of the photosensitive resin composition excellent in plating adhesion, and the upper limit of the SP value of the component (D) is 13 (cal/cm 3)1/2 or less, preferably 12.9 (cal/cm 3)1/2 or less, more preferably 12.8 (cal/cm 3)1/2 or less; the SP value can be calculated using Fedors theory).
As the component (D), a polymer having an SP value within the above range and insoluble in a developer can be used. Examples of such a polymer include acrylic polymers having an SP value of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less).
The acrylic polymer is preferably a copolymer containing a structural unit derived from an oxyalkylene group-containing alkyl (meth) acrylate monomer and a structural unit derived from an alkyl (meth) acrylate monomer, from the viewpoint of obtaining a cured product excellent in plating adhesion.
The number of carbon atoms of the oxyalkylene group-containing alkyl (meth) acrylate monomer is preferably 2 or 3, more preferably 2. The number of repeating units of the oxyalkylene group is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, preferably 50 or less, more preferably 40 or less, further preferably 30 or less.
The number of carbon atoms of the acryl group of the alkyl (meth) acrylate monomer is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, preferably 22 or less, more preferably 21 or less, further preferably 20 or less.
The acrylic polymer may be a copolymer containing structural units derived from a vinyl ether monomer in addition to structural units derived from an oxyalkylene-containing alkyl (meth) acrylate monomer and structural units derived from an alkyl (meth) acrylate monomer.
The number of carbon atoms of the acryl group of the vinyl ether monomer is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, preferably 22 or less, more preferably 21 or less, further preferably 20 or less.
As the component (D), a copolymer having a structural unit represented by the formula (D-1) and a structural unit represented by the following formula (D-2) is preferable:
[ chemical formula 7]
In the formula (D-1), R 1 independently represents a hydrogen atom or a methyl group, and R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; p independently represents an integer of 2 to 4, and q represents an integer of 2 to 100;
In the formula (D-2), R 3 independently represents a hydrogen atom or a methyl group, and R 4 independently represents an alkyl group having 1 to 22 carbon atoms.
The structural unit represented by the formula (D-1) is a structural unit derived from an oxyalkylene-containing alkyl (meth) acrylate monomer. The structural unit represented by the formula (D-2) is a structural unit derived from an alkyl (meth) acrylate monomer.
R 1 and R 3 each independently represent a hydrogen atom or a methyl group, preferably a hydrogen atom.
R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6. Examples of the alkyl group represented by R 2 include: methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, neopentyl, tert-pentyl, sec-pentyl, 2-ethylhexyl, and the like.
R 4 independently represents an alkyl group having 1 to 22 carbon atoms, and the same meaning as the alkyl group having 1 to 22 carbon atoms represented by R 2.
P independently represents an integer of 2 to 4, preferably 2 or 3, more preferably 2.
Q represents the number of repeating alkylene oxide groups and an integer of 2 to 100. q is preferably an integer of 3 to 50.
As the component (D), the ratio of the structural unit represented by the formula (D-1) to the structural unit represented by the formula (D-2) (structural unit represented by the formula (D-1): structural unit represented by the formula (D-2)) is preferably 5:95 to 80:20.
The component (D) may be a copolymer comprising a structural unit represented by the formula (D-3) in addition to the structural unit represented by the formula (D-1) and the structural unit represented by the formula (D-2). The structural unit represented by the formula (3) is a structural unit derived from a vinyl ether monomer;
[ chemical formula 8]
In the formula (D-3), R 5 represents an alkyl group having 2 to 22 carbon atoms.
R 5 represents an alkyl group having 2 to 22 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear. The number of carbon atoms of the alkyl group is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6. Examples of the alkyl group represented by R 5 include: methyl, ethyl, n-butyl, isobutyl, tert-butyl, octyl, nonyl, decyl, undecyl, dodecyl, hexyl, octadecyl, propyl, isopropyl, 2-ethylhexyl, cyclohexyl and the like.
(D) When the component (C) is a copolymer comprising a structural unit represented by the formula (D-3), the content ratio (structural unit represented by the formula (D-1) and structural unit represented by the following formula (D-2): structural unit represented by the formula (D-3)) is preferably 100:1 to 45, more preferably 100:5 to 40.
The component (D) may be a copolymer further comprising structural units other than the structural unit represented by the formula (D-1), the structural unit represented by the following formula (D-2), and the structural unit represented by the formula (D-3) (structural units other than the structural units represented by the formulas (D-1) to (D-3)), as required.
(D) When the component (A) is a copolymer comprising structural units other than the structural units represented by the formulae (D-1) to (D-3), the content ratio (structural units represented by the formulae (D-1) to (D-3): structural units other than the structural units represented by the formulae (D-1) to (D-3)) is preferably 100:1 to 40.
The component (D) can be produced, for example, by copolymerizing an oxyalkylene group-containing alkyl (meth) acrylate monomer represented by the following formula (D-1 a) and an alkyl (meth) acrylate monomer represented by the following formula (D-2 a),
[ Chemical formula 9]
In the formula (D-1 a), R 1a independently represents a hydrogen atom or a methyl group, and R 2a represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; r independently represents an integer of 2 to 4, and s represents an integer of 2 to 100;
In the formula (D-2 a), R 3a independently represents a hydrogen atom or a methyl group, and R 4a represents an alkyl group having 1 to 22 carbon atoms.
R 1a each independently represents a hydrogen atom or a methyl group, and is the same as R 1 in the formula (D-1). R 3a independently represents a hydrogen atom or a methyl group, and the same meaning as R 3 in formula (D-2).
R 2a represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and is the same as R 2 in the formula (D-1).
R 4a represents an alkyl group having 1 to 22 carbon atoms, and the same meaning as R 4 in formula (D-2).
R independently represents an integer of 2 to 4, and is the same as p in formula (D-1).
S represents an integer of 2 to 100, and is the same as q in the formula (D-1).
Examples of the oxyalkylene-containing alkyl (meth) acrylate monomer represented by the formula (D-1 a) include: polyethylene glycol (meth) acrylate (ethylene glycol) having a polymerization number of 2 to 100), polypropylene glycol (propylene glycol) having a polymerization number of 2 to 100, poly (ethylene-propylene) glycol (ethylene-propylene) having a polymerization number of 2 to 100, poly (ethylene-tetramethylene) glycol (ethylene-tetramethylene) having a polymerization number of 2 to 100, poly (ethylene-propylene) glycol (ethylene glycol) having a polymerization number of 2 to 100, poly (methoxypolypropylene glycol) having a polymerization number of 2 to 100, poly (ethylene-propylene) glycol (propylene glycol) having a polymerization number of 2 to 100, methoxypolyethylene-propylene) glycol (ethylene-propylene) having a polymerization number of 2 to 100, poly (ethylene-tetramethylene) glycol (ethylene-tetramethylene) having a polymerization number of 2 to 100, butoxypoly (ethylene-propylene) glycol (ethylene-propylene) having a polymerization number of 2 to 100, poly (ethylene-propylene) glycol (ethylene-propylene) having a polymerization number of 2 to 100, and poly (ethylene-propylene) having a polymerization number of 2 to 100, polyethylene-propylene (ethylene-propylene) glycol (ethylene-propylene) having a polymerization number of 2 to 100, polyethylene-propylene (ethylene-propylene) having a polymerization number of oxypropylene (ethylene-propylene) glycol (ethylene-propylene) having a polymerization number of 2 to 100, ether group-containing alkyl (meth) acrylates such as stearyl-oxy polyethylene glycol (ethylene glycol polymerization number of 2 to 100) esters and phenoxy polyethylene glycol (ethylene glycol polymerization number of 2 to 100) esters of (meth) acrylic acid.
Examples of the alkyl (meth) acrylate monomer represented by the formula (D-2 a) include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isoundecyl (meth) acrylate, isododecyl (meth) acrylate, neopentyl (meth) acrylate, t-amyl (meth) acrylate, sec-amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. As the alkyl (meth) acrylate monomer, they may be used alone or in combination of plural ones.
When the total amount of the oxyalkylene group-containing alkyl (meth) acrylate monomer and the alkyl (meth) acrylate monomer is set to 100 parts by mass, the oxyalkylene group-containing alkyl (meth) acrylate monomer is preferably used in an amount of 5 to 80 parts by mass.
When the total amount of the oxyalkylene-containing alkyl (meth) acrylate monomer and the alkyl (meth) acrylate monomer is set to 100 parts by mass, the alkyl (meth) acrylate monomer is preferably used in an amount of 20 parts by mass or more and 95 parts by mass or less.
The component (D) can be produced by copolymerizing a vinyl ether monomer represented by the following formula (D-3 a) in addition to the oxyalkylene group-containing alkyl (meth) acrylate monomer and the alkyl (meth) acrylate monomer;
[ chemical formula 10]
H2C＝CH-O-R5a (D-3a)
In the formula (D-3 a), R 5a represents an alkyl group having 2 to 22 carbon atoms.
R 5a represents an alkyl group having 2 to 22 carbon atoms, and is the same as R 5 in the formula (D-3).
Examples of the vinyl ether monomer represented by the formula (D-3 a) include: alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-or t-butyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, undecyl vinyl ether, dodecyl vinyl ether, hexa vinyl ether, octadecyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether, and the like. As the vinyl ether monomer, they may be used alone or in combination of plural ones.
When vinyl ether monomer is copolymerized, the ratio of the amounts is: the mass ratio of the "total amount of the oxyalkylene group-containing alkyl (meth) acrylate monomer and the alkyl (meth) acrylate monomer" to the "vinyl ether monomer" (total amount of the oxyalkylene group-containing alkyl (meth) acrylate monomer and the alkyl (meth) acrylate monomer: vinyl ether monomer) is preferably 100:1 to 45, more preferably 100:5 to 40.
The component (D) may be produced by copolymerizing a monomer other than the oxyalkylene group-containing alkyl (meth) acrylate monomer, the alkyl (meth) acrylate monomer, and the vinyl ether monomer, as required.
Examples of such monomers include: (meth) acrylic acid as acrylic acid or methacrylic acid; aralkyl (meth) acrylates such as hydroxyalkyl (meth) acrylate, benzyl acrylate, polycaprolactone-modified hydroxyalkyl acrylate or methacrylate, phenoxyethyl (meth) acrylate, and the like; (meth) acrylamides such as acrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, acryloylmorpholine; aromatic hydrocarbon vinyl compounds such as styrene, α -methylstyrene, chlorostyrene, and vinyltoluene; vinyl esters such as vinyl acetate and vinyl propionate; allyl compounds such as diallyl phthalate; aliphatic hydrocarbon vinyl compounds such as vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, and fluoroolefin maleimide, and these may be used alone or in combination of two or more.
When such monomers are copolymerized, the ratio of the amounts thereof is: the mass ratio of the "total amount of the oxyalkylene group-containing (meth) acrylic acid alkyl ester monomer, the (meth) acrylic acid alkyl ester monomer and the vinyl ether monomer" to the "monomer" (total amount of the oxyalkylene group-containing (meth) acrylic acid alkyl ester monomer, the (meth) acrylic acid alkyl ester monomer and the vinyl ether monomer: the monomer) is preferably used in the range of 100:1 to 40.
Examples of the method for synthesizing the component (D) include: emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and the like. Specifically, random copolymerization is performed by dropping each monomer as a copolymerization component into a solvent in the presence of a radical polymerization initiator and heating the same. Alternatively, the monomers as the copolymerization components may be produced by sequentially dropping the monomers into a solvent in the presence of a block copolymerization initiator and heating the mixture to block the monomers. (D) The component may be any of random copolymer, block copolymer and graft copolymer.
The radical polymerization initiator is not particularly limited as long as it is an initiator generally used for radical polymerization. Examples of the radical polymerization initiator include peroxides and azo compounds, and examples thereof include PERBUTYL D, PERBUTYL O, PEROCTA O, and the like manufactured by the company solar oil. Further, the block initiator may be a 2-stage decomposition type difunctional initiator, for example, 1-bis- (t-butylperoxy) -2-methylcyclohexane, or the like.
(D) The components may be commercially available ones. Examples of the commercial products include "POLYFLOW WS-314", "POLYFLOW No.99C", "POLYFLOW No.77" and "POLYFLOWNo.75" manufactured by Co-ordinated chemical Co., ltd.
The weight average molecular weight of the component (D) is preferably 3000 or more, more preferably 3500 or more, further preferably 4000 or more, preferably 500000 or less, more preferably 50000 or less, further preferably 25000 or less, from the viewpoint of remarkably obtaining the effect of the present invention. The weight average molecular weight can be measured by Gel Permeation Chromatography (GPC) as a polystyrene equivalent value.
When the nonvolatile content of the photosensitive resin composition is set to 100% by mass, the content of the component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, from the viewpoint of improving the plating adhesion.
From the viewpoint of remarkably obtaining the effect of the present invention, the mass ratio of the component (D) to the epoxy resin (mass%) of the component (D) when the nonvolatile component of the photosensitive resin composition is 100 mass%)/mass (mass%)) of the component (a) when the nonvolatile component of the photosensitive resin composition is 100 mass%)) is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit is preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less.
From the viewpoint of remarkably obtaining the effect of the present invention, the mass ratio of the (D) component to the (B) resin containing a carboxyl group and an olefinic double bond (mass%) of the (D) component when the nonvolatile component of the photosensitive resin composition is 100 mass%)/mass (mass%) of the (B) component when the nonvolatile component of the photosensitive resin composition is 100 mass%) is preferably 0.001 or more, more preferably 0.005 or more, and still more preferably 0.01 or more. The upper limit is preferably 1 or less, more preferably 0.1 or less, and still more preferably 0.05 or less.
From the viewpoint of remarkably obtaining the effect of the present invention, the mass ratio of the component (D) to the photopolymerization initiator (mass%) of the component (D) when the nonvolatile component of the photosensitive resin composition is 100 mass%)/mass (mass%) of the component (C) when the nonvolatile component of the photosensitive resin composition is 100 mass%)) is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. The upper limit is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less, 5 or less, 1 or less, 0.5 or less, and 0.1 or less.
Inorganic filler with average particle diameter below 100nm
The photosensitive resin composition of the present invention may contain (E) an inorganic filler having an average particle diameter of 100nm or less as an optional component. (E) The inorganic filler is contained in the photosensitive resin composition in the form of particles.
The average particle diameter of the component (E) is 100nm or less, preferably 90nm or less, more preferably 80nm or less, preferably 5nm or more, more preferably 10nm or more, from the viewpoint of suppressing light reflection at the time of exposure and obtaining excellent core formation property and developability.
The average particle size of the inorganic filler material can be determined by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle diameter can be measured as the average particle diameter. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of methyl ethyl ketone into a vial and dispersing the mixture with ultrasonic waves for 10 minutes was used. For the measurement sample, a laser diffraction type particle size distribution measuring device was used, the wavelength of the laser light source was set to blue and red, the volume-based particle size distribution of the inorganic filler was measured by a flow cell method, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
The specific surface area of the component (E) is preferably 1m 2/g or more, more preferably 3m 2/g or more, particularly preferably 5m 2/g or more, from the viewpoint of suppressing light reflection at the time of exposure and obtaining excellent core formation properties. The upper limit is not particularly limited, but is preferably 60m 2/g or less, 50m 2/g or less, or 40m 2/g or less. The specific surface area can be obtained by adsorbing nitrogen gas onto the surface of a sample according to the BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH corporation) and calculating the specific surface area using the BET multipoint method.
As the material of the component (E), an inorganic compound is used. Examples of the material of the component (E) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as silica. (E) The components may be used alone or in combination of at least 2 kinds in any ratio.
(E) The components may be commercially available ones. Examples of such commercial products include "ADMANANO series" manufactured by elegant Dou Ma (Admatechs) such as Y50SZ-AM1, etc., a "UFP series" manufactured by electric chemical industry Co., ltd., a "Sciqas series" manufactured by Sakai chemical industry Co., ltd., a "SEAHOSTAR series" manufactured by Japanese catalyst Co., ltd., and a "BF series" manufactured by chemical industry Co., ltd.
From the viewpoint of improving moisture resistance and dispersibility, the component (E) is preferably treated with a surface treatment agent. Examples of the surface treating agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of 1 or more than 2 kinds.
Examples of the commercial product of the surface treatment agent include: "KBM403" by Xinyue chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" by Xinyue chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" by Xinyue chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" by Xinyue chemical industry Co., ltd. (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" by Xinyue chemical industry Co., ltd. (hexamethyldisilazane), "KBM103" by Xinyue chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" by Xinyue chemical industry Co., ltd. (long-chain epoxy silane coupling agent), and "KBM-7103" Xinyue chemical industry Co., ltd. (3, 3-trifluoropropyl trimethoxysilane) are disclosed.
The degree of surface treatment with the surface treatment agent preferably falls within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface treatment agent, more preferably 0.2 to 3 mass%, and even more preferably 0.3 to 2 mass%.
The degree of surface treatment based on the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m 2 or more, more preferably 0.1mg/m 2 or more, and still more preferably 0.2mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition or in melt viscosity in the form of a sheet, the content is preferably 1.0mg/m 2 or less, more preferably 0.8mg/m 2 or less, and still more preferably 0.5mg/m 2 or less.
(E) The carbon amount per unit surface area of the component can be measured after the inorganic filler after the surface treatment is subjected to a cleaning treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treating agent, and the mixture was ultrasonically cleaned at 25 ℃ for 5 minutes. After removing the supernatant and drying the solid component, a carbon analyzer may be used to determine the amount of carbon per unit surface area of the inorganic filler material. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
When the nonvolatile content in the photosensitive resin composition is set to 100% by mass, the content of the component (E) is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, from the viewpoint of significantly obtaining the effect of the present invention.
Reactive diluent (F)
The photosensitive resin composition of the present invention may contain (F) a reactive diluent as an optional component. The (F) reactive diluent as the component (F) does not include the components belonging to the above-mentioned components (A) to (E). (F) The components may be used alone or in combination of 1 or more than 2.
By incorporating the reactive diluent (F) in the photosensitive resin composition, photoreactivity can be improved. As the (F) reactive diluent, for example, a (meth) acrylate compound having 1 or more (meth) acryloyl groups in 1 molecule (preferably 2 or more) can be used.
Typical (meth) acrylate compounds include, for example: hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; monoacrylates or diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; polyhydric alcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol, and polyhydric acrylic esters of adducts of ethylene oxide, propylene oxide and epsilon-caprolactone; phenols such as phenoxy acrylate and phenoxy ethyl acrylate, and acrylates such as ethylene oxide or propylene oxide adducts; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether; modified epoxy acrylates; melamine acrylates; and/or methacrylates corresponding to the above acrylates. Among these, preferred are polyvalent acrylates or polyvalent methacrylates, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO-added tri (meth) acrylate, glycerol PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrahydrofurfuryl alcohol oligo (meth) acrylate, ethylcarbinol oligo (meth) acrylate, 1, 4-butanediol oligo (meth) acrylate, 1, 6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N ', N' -tetra (beta-hydroxyethyl) ethylenediamine (meth) acrylate, and as ternary or higher acrylates or methacrylates, tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, tri (3-hydroxypropyl) phosphate, tri (meth) hydroxypropyl (3-hydroxypropyl) phosphate, etc, phosphotriester (meth) acrylates such as bis (3- (meth) acryl-2-hydroxyoxypropyl) (2- (meth) acryloyloxyethyl) phosphate and (3- (meth) acryl-2-hydroxyoxypropyl) bis (2- (meth) acryloyloxyethyl) phosphate. These photosensitive (meth) acrylate compounds may be used singly or in combination of two or more. "EO" refers to ethylene oxide.
(F) As the reactive diluent, commercially available ones can be used. Examples of the commercial products include "DPHA" manufactured by Japanese chemical Co., ltd., and "EBECRYL3708" manufactured by DAICEL-ALLNEX Co., ltd.
(F) Reactive diluents typically have low viscosity. (F) The specific viscosity of the reactive diluent is typically less than 0.5 Pa-s. (F) The lower viscosity limit of the reactive diluent is not particularly limited, and may be, for example, 0.001pa·s or more, 0.005pa·s or more, 0.01pa·s or more, or the like. (F) The viscosity of the reactive diluent can be measured at 25.+ -. 2 ℃ using an E-type viscometer.
The content of the reactive diluent (F) is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 20 mass% or more, preferably 40 mass% or less, more preferably 35 mass% or less, further preferably 30 mass% or less, based on 100 mass% of the nonvolatile component in the photosensitive resin composition, from the viewpoint of promoting photocuring.
Solvent (G)
The photosensitive resin composition may contain a solvent (G) as a volatile component in combination with the nonvolatile components such as the components (a) to (F). The viscosity of the photosensitive resin composition can be adjusted by using the (G) solvent as the (G) component. Examples of the solvent (G) include organic solvents.
Examples of the solvent (G) include: ketone solvents such as ethyl methyl 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 cellosolve acetate, carbitol acetate, and ethyl carbitol acetate (ethyl diglycol acetate); ether ester solvents such as propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyldiglycol acetate, gamma-butyrolactone, methyl methoxypropionate, and the like; aliphatic hydrocarbon solvents such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha and solvent naphtha. (G) The solvent may be used alone or in combination of 1 or more than 2.
The amount of the solvent (G) is preferably appropriately adjusted from the viewpoint of coatability of the photosensitive resin composition.
(H) optional additives
The photosensitive resin composition of the present invention may further contain any additive (H) as any component in combination with the components (a) to (G) within a range that does not significantly impair the effects of the present invention. The additive (H) does not include any of the above components (A) to (G). (H) Any additive may be used alone or in combination of 1 or more than 2.
Examples of the optional additive (H) include: photosensitizers, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial agents, antifoaming agents, leveling agents, thickening agents, adhesion-imparting agents, thixotropic-imparting agents, release agents, surface-treating agents, dispersants, surface-modifying agents, stabilizers, and the like.
The photosensitive resin composition can be produced as follows: the components (a) to (D) as essential components are mixed and the components (E) to (H) as optional components are appropriately mixed, and if necessary, kneaded or stirred by a kneading means such as a three-roll mill, a ball mill, a bead mill, a sand mill, or a stirring means such as a super stirrer, a planetary stirrer, or a high-speed rotary stirrer, to thereby produce a resin varnish.
< Properties and uses of photosensitive resin composition >
The photosensitive resin composition can be used for forming a core layer of an optical waveguide. The core layer formed generally contains a cured product of the photosensitive resin composition. The photosensitive resin composition can be generally cured by light, preferably by light and heat. In general, the solvent (G) is a volatile component among the components contained in the photosensitive resin composition, and therefore the volatile component can be volatilized by heat at the time of curing, and the other non-volatile components cannot be volatilized by heat at the time of curing. Accordingly, the cured product of the photosensitive resin composition may contain a nonvolatile component of the photosensitive resin composition or a reaction product thereof. The core layer preferably contains only a cured product of the photosensitive resin composition.
The photosensitive resin composition contains components (a) to (D) in combination, and therefore exhibits excellent core formability. Specifically, when the photosensitive resin composition is exposed and developed to form a line layer corresponding to the core layer, a line layer having a small minimum formation width can be formed. For example, the photosensitive resin composition is exposed and developed to form line layers having L/S (line width/line spacing) of 10 μm/10 μm, 5 μm/5 μm and 3 μm/3 μm. In this case, the aspect ratio of the wire layer may be preferably 0.6 or more, more preferably 0.8 or more in any wire layer. Here, L (line width) in L/S represents the width of the line layer, and S (line spacing) represents the interval between lines. In addition, the aspect ratio of the line layer indicates the ratio expressed as "layer thickness/line width" of the line layer. According to the photosensitive resin composition having such excellent core formability, a core layer having a small width and small spacing can be formed, and miniaturization of an optical waveguide can be achieved. The measurement of the minimum formation width can be performed by the method described in examples described below.
Since the photosensitive resin composition contains the components (a) to (D) in combination, the composition generally exhibits a characteristic of excellent plating adhesion even when the surface of the cured photosensitive resin composition after roughening treatment has a low arithmetic average roughness (Ra). Therefore, even if the surface irregularities provided on the core layer are small, a cured product excellent in plating adhesion can be obtained. The surface of the cured photosensitive resin composition after the roughening treatment preferably has an arithmetic average roughness (Ra) of 500nm or less, more preferably less than 400nm, still more preferably 200nm or less, and still more preferably less than 200nm. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The arithmetic average roughness (Ra) can be measured by the method described in examples described below.
The photosensitive resin composition contains components (a) to (D) in combination, and therefore exhibits excellent peel strength from the plated conductor layer. Specifically, after the photosensitive resin composition is cured, the cured photosensitive resin composition is roughened. The roughened surface was subjected to copper plating treatment, and a conductor layer was formed on the cured photosensitive resin composition to obtain a sample. The sample was used to measure peel strength. In this case, the peel strength is preferably 0.2kgf/cm or more, more preferably 0.3kgf/cm or more. The upper limit is not particularly limited, and may be 10kgf/cm or less. The peel strength can be measured by the method described in examples below.
The photosensitive resin composition contains components (a) to (D) in combination, and therefore exhibits a characteristic of being able to reduce light transmission loss. Specifically, a test substrate having a coating layer and a core layer formed using a photosensitive resin composition was produced. The test substrate was used to measure optical transmission loss. At this time, the optical transmission loss is preferably less than 2dB/cm, more preferably less than 1dB/cm. The lower limit is not particularly limited, and may be 0dB/cm or more, 0.1dB/cm or more, or the like. The optical transmission loss can be measured by the method described in examples described below.
Since the photosensitive resin composition contains components (a) to (D) in combination, it generally exhibits a characteristic that a cured product excellent in absorbance at 1310nm can be obtained. Specifically, a photosensitive resin composition solution is prepared by dissolving a photosensitive resin composition in a solvent. The absorbance of the photosensitive resin composition solution at 1310nm was measured using an ultraviolet-visible near-infrared spectrophotometer. In this case, the absorbance is preferably less than 0.0100, more preferably less than 0.0050, and still more preferably less than 0.0025. The lower limit is not particularly limited, and may be set to 0.0001 or more. The absorbance can be measured by the method described in examples below.
The photosensitive resin composition of the present invention can remove non-exposed portions not irradiated with light by using a developer. In particular, the photosensitive resin composition of the present invention can be satisfactorily removed by using a sodium carbonate solution as an alkali developer. Therefore, the photosensitive resin composition of the present invention can be suitably used for sodium carbonate development.
The photosensitive resin composition of the present invention is excellent in core formability and can reduce light transmission loss, and therefore can be suitably used as a photosensitive resin composition for forming a core layer of an optical waveguide. Thus, the photosensitive resin composition of the present invention can be suitably used for the production of a core layer of an optical waveguide (photosensitive resin composition for forming a core layer of an optical waveguide), and for the formation of an optical waveguide capable of transmitting light having a wavelength of 1300nm to 1320nm (photosensitive resin composition for the formation of an optical waveguide capable of transmitting light having a wavelength of 1300nm to 1320 nm). The photosensitive resin composition of the present invention is preferably used for forming a single-mode optical waveguide, preferably for forming a single-mode optical waveguide for light having a wavelength of 1310nm, for example.
[ Resin sheet ]
The photosensitive resin composition of the present invention can be suitably used in the form of a resin sheet obtained by forming a photosensitive resin composition layer on a support. In other words, the resin sheet includes a support and a photosensitive resin composition layer provided on the support, the photosensitive resin composition layer being formed from the photosensitive resin composition of the present invention.
Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl acetate film, and polyethylene terephthalate film is particularly preferred.
Examples of the commercially available support include: examples of the polyethylene terephthalate film include, but are not limited to, polypropylene films such as "ALPHAN MA-410" manufactured by the company of making prince paper, "E-200C" manufactured by the company of making Xinyue film, and PS-series polyethylene terephthalate films such as "PS-25" manufactured by the company of emperor. In order to facilitate removal of the photosensitive resin composition layer, these supports may be coated with a release agent such as a silicone coating agent on the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. When the thickness is set to 5 μm or more, breakage of the support can be suppressed at the time of support detachment before development, and when the thickness is set to 50 μm or less, resolution at the time of exposure from above the support can be improved. In addition, a support with a low white point (fish eye) is preferable. Here, white point means: when a film is produced by kneading, extruding, biaxial stretching, casting or the like of a material by hot melting, foreign substances, undissolved substances, oxidized deteriorated substances or the like of the material are mixed in the film.
In addition, the support is preferably excellent in transparency in order to reduce light scattering at the time of exposure with active light such as ultraviolet rays. Specifically, the haze (haze standardized in JIS-K6714) of the support, which is an index of transparency, is preferably 0.1 to 5. Further, the photosensitive resin composition layer may be protected by a protective film.
By protecting the photosensitive resin composition layer side of the resin sheet with the protective film, adhesion of dirt and the like to the surface of the photosensitive resin composition layer can be prevented from being damaged. As the protective film, a film made of the same material as the support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. The thickness of 1 μm or more can improve the handleability of the protective film, and the thickness of 40 μm or less tends to improve the cost effectiveness. The protective film is preferably formed by: the adhesion between the photosensitive resin composition layer and the protective film is smaller than the adhesion between the photosensitive resin composition layer and the support.
The resin sheet can be produced as follows: for example, the photosensitive resin composition of the present invention is dissolved in an organic solvent to prepare a resin varnish, the resin varnish is applied on a support, and the organic solvent is dried by heating or blowing hot air, etc., to form a photosensitive resin composition layer. Specifically, a resin sheet can be produced by first completely removing bubbles in a photosensitive resin composition by a vacuum degassing method or the like, then coating the photosensitive resin composition on a support, removing a solvent by a hot air furnace or a far infrared ray furnace, and drying the same, and then, if necessary, laminating a protective film on the obtained photosensitive resin composition layer. The specific drying conditions also vary depending on the curability of the photosensitive resin composition and the amount of the organic solvent in the resin varnish, and the resin varnish containing 30 to 60 mass% of the organic solvent may be dried at 80 to 120 ℃ for 3 to 13 minutes. The amount of the organic solvent remaining in the photosensitive resin composition layer is preferably 5 mass% or less, more preferably 2 mass% or less, relative to the total amount of the photosensitive resin composition layer, from the viewpoint of preventing the organic solvent from diffusing in the subsequent step. The person skilled in the art can appropriately set the appropriate drying conditions by simple experiments.
The thickness of the photosensitive resin composition layer is preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, and preferably 15 μm or less, more preferably 13 μm or less, further preferably 10 μm or less, from the viewpoint of improving the handleability and suppressing the decrease in sensitivity and resolution inside the photosensitive resin composition layer.
Examples of the application method of the photosensitive resin composition include a gravure application method, a micro gravure application method, a reverse application method, a kiss reverse application method, a die application method, a slot die method, a lip application method, a comma application method, a blade application method, a roll application method, a knife application method, a curtain application method, a cavity gravure application method, a slot method, a spray application method, and a dip application method.
The photosensitive resin composition may be applied in a plurality of steps, or may be applied in a single step, or may be applied by combining a plurality of steps. Among them, a die coating (die coater) method excellent in uniformity of coating is preferable. In order to avoid contamination of foreign matter, it is preferable to perform the coating step in an environment where foreign matter such as a clean room is less likely to occur.
[ Photosensitive resin composition Package packing ]
The photosensitive resin composition of the present invention can be suitably used as a photosensitive resin composition for forming a core layer of an optical waveguide. Thus, the photosensitive resin composition set includes the photosensitive resin composition of the present invention and a photosensitive resin composition for coating. The photosensitive resin composition package is useful for the production of an optical waveguide having a core layer containing a cured product of the photosensitive resin composition of the present invention and a cladding layer containing a cured product of a cladding photosensitive resin composition. The photosensitive resin composition for coating may be any known photosensitive resin composition. Since the photosensitive resin composition of the present invention and the photosensitive resin composition for coating are both photosensitive, a fine optical waveguide can be produced with high efficiency by a method including exposure and development.
[ Optical waveguide ]
The photosensitive resin composition, the resin sheet and the photosensitive resin composition set can be used for manufacturing optical waveguides. Hereinafter, embodiments of the optical waveguide will be described with reference to the drawings.
Fig. 1 is a perspective view schematically showing an optical waveguide 10 according to an embodiment of the present invention. As shown in fig. 1, the optical waveguide 10 includes a core layer 100 and a cladding layer 200. The core layer 100 preferably contains only the cured product of the photosensitive resin composition of the present invention. The coating layer 200 preferably contains only a cured product of the coating resin composition. As the coating resin composition, a resin composition that can obtain a cured product having a lower refractive index than the cured product of the photosensitive resin composition of the present invention can be used. As the coating resin composition, a photocurable resin composition or a thermosetting resin composition may be used.
The core layer 100 is disposed in the cladding layer 200. Thus, the core layer 100 is covered with the clad layer 200. Generally, the entire outer peripheral surface of the core layer 100 is covered with the clad layer 200. The core layer 100 is in direct contact with the clad layer 200 without other layers interposed therebetween, and thus, the interface 100I may be formed between the core layer 100 and the clad layer 200. In general, the core layer 100 has a higher refractive index than the clad layer 200, and thus, light (not shown) can be transmitted from one end (one end on the incident side) 100A to the other end (one end on the emission side) 100B of the core layer 100 within the core layer 100.
The wavelength of light that the optical waveguide 10 is capable of transmitting can be variously selected. By way of example, the preferred wavelength range of the transmitted light may be 840nm to 860nm (e.g., 850 nm), 1300nm to 1320nm (e.g., 1310 nm), 1540nm to 1560nm (e.g., 1550 nm), and the like. Among them, the wavelength range of the light transmitted in the light transmission path 10 is preferably 1300nm to 1320nm.
The optical waveguide 10 may be a single-mode optical waveguide, or may be a multimode optical waveguide, and is preferably a single-mode optical waveguide. Among them, the optical waveguide 10 is preferably a single-mode optical waveguide for light in the aforementioned preferable wavelength range. For example, the optical waveguide 10 is preferably a single mode optical waveguide for 1310nm light.
The width L of the core layer 100 is desirably set appropriately in a range capable of transmitting light. 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, particularly preferably 2 μm or more, and is preferably 50 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less, and may be 10 μm or less or 5 μm or less. The width L of the core layer 100 corresponds to the line width (line width) of the core layer 100 when viewed from the thickness direction.
The interval S of the core layer 100 is desirably set appropriately in a range capable of transmitting light. The specific range of the spacing S of the core layer 100 is preferably 50 μm or more, more preferably 70 μm or more, particularly preferably 100 μm or more, and is preferably 1000 μm or less, more preferably 500 μm or less, particularly preferably 300 μm or less. The interval S of the core layers 100 corresponds to the interval (pitch) of the core layers as viewed from the thickness direction.
The thickness T of the core layer 100 is desirably set appropriately in a range capable of transmitting light. The specific range of the thickness T of the core layer 100 is preferably 0.5 μm or more, more preferably 1 μm or more, particularly preferably 2 μm or more, and is preferably 50 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less, and may be 10 μm or less.
The thickness of the cladding layer 200 is typically greater than the thickness of the core layer 100. The specific thickness of the coating layer 200 is preferably 5 μm or more, more preferably 7 μm or more, particularly preferably 10 μm or more, and is preferably 40 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less.
The optical waveguide 10 may include any element other than the core layer 100 and the cladding layer 200 as needed. For example, the optical waveguide 10 may include a conductor layer (not shown) formed by plating or the like on the core layer, and the base material 300. In the optical waveguide 10 including the substrate 300, the cladding layer 200 is generally provided on the substrate 300, and the core layer 100 is provided in the cladding layer 200.
As the base material 300, a hard substrate such as a glass substrate, a metal substrate, a ceramic substrate, a wafer, or a circuit substrate can be used. As the 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, or a silicon carbide (SiC) wafer may be used, or a pseudo wafer may be used. As the pseudo wafer, for example, a plate-like member having a mold resin and electronic components embedded in the mold resin can be used. Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. The circuit board herein means: a substrate having a patterned conductor layer (circuit) formed on one or both surfaces of the substrate. Further, as the substrate 300, a film formed of a plastic material such as polyethylene terephthalate, polyimide, or polyester may be used. Further, a flexible circuit substrate may be employed as the substrate 300.
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 element. The protective layer may be provided so as to cover, for example, a surface of the clad layer 200 opposite to the base material 300.
As described above, the optical waveguide 10 can have a small transmission loss. Further, since the core layer 100 of the optical waveguide 10 has excellent core formability, it is possible to suppress the occurrence of surface irregularities, and at the same time, it is possible to realize fine wiring of the core layer, and it is possible to form the optical waveguide with the line width L small as described above.
The optical waveguide 10 can be produced using the photosensitive resin composition of the present invention. For example, the optical waveguide 10 can be manufactured by a method including the following steps in order:
A step (I) of forming a first composition layer containing a coating resin composition,
A step (II) of curing the first composition layer,
A step (III) of forming a second composition layer containing the photosensitive resin composition of the present invention on the first composition layer, a step (IV) of exposing the second composition layer to light,
A step (V) of developing the second composition layer,
A step (VI) of curing the second composition layer,
A step (VIII) of forming a third composition layer containing a coating resin composition on the second composition layer, and a step (IX) of curing the third composition layer. Further, the method may include a step (VII) of forming a conductor layer on the core layer after the step (VI) is completed and before the step (VIII), if necessary.
Fig. 2 is a schematic cross-sectional view illustrating a process (I) of a method for manufacturing an optical waveguide according to an embodiment of the present invention. As shown in fig. 2, a method for manufacturing an optical waveguide according to an embodiment of the present invention includes: and (I) forming a first composition layer 210 containing the photosensitive resin composition for coating. In this embodiment, an example of forming the first composition layer 210 on the substrate 300 is illustrated.
The method of forming the first composition layer 210 is not particularly limited. For example, the first composition layer 210 may 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 coated.
Examples of the coating method include a gravure coating method, a micro gravure coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a plate coating method, a roll coating method, a knife coating method, a curtain coating method, a cavity gravure coating method, a slot method, a spin coating method, a slit coating method, a spray coating method, a dip coating method, a hot melt coating method, a bar coating method, an applicator method, an air knife coating method, a curtain coating method, an offset printing method, a brush coating method, and a screen printing method.
The coating resin composition may be applied once or may be applied in a plurality of times. In addition, different coating modes can be combined and implemented. In order to avoid the contamination of foreign matter, the coating is preferably performed in an environment where foreign matter such as a clean room is less likely to occur.
After the coating resin composition is applied, the first composition layer 210 may be dried as needed. Drying can be performed by a drying device such as a hot blast stove or a far infrared oven. The drying conditions are preferably set appropriately according to the composition of the coating resin composition. The drying temperature is preferably 50℃or higher, more preferably 70℃or higher, particularly preferably 80℃or higher, and is preferably 150℃or lower, more preferably 130℃or lower, particularly preferably 120℃or lower. The drying time is preferably 30 seconds or more, more preferably 60 seconds or more, particularly preferably 120 seconds or more, and is preferably 60 minutes or less, more preferably 20 minutes or less, particularly preferably 5 minutes or less.
The first composition layer 210 can be formed using, for example, a coating resin sheet including a "support" and a "coating photosensitive resin composition layer including a coating photosensitive resin composition". Specifically, the first composition layer 210 can be formed on the substrate 300 by laminating the photosensitive resin composition layer for coating of the resin sheet for coating on the substrate 300. Lamination is generally performed by crimping a photosensitive resin composition layer for coating a resin sheet to the base material 300 while heating. The lamination is preferably performed using a vacuum lamination method and under reduced pressure. In addition, before lamination, a preheating treatment of heating the resin sheet and the base material may be performed as needed.
The lamination conditions may be carried out, for example, at a pressure bonding temperature (lamination temperature) of 70 to 140℃and a pressure bonding pressure of 1kgf/cm 2～11kgf/cm2(9.8×104N/m2～107.9×104N/m2 for 5 to 300 seconds. The lamination is preferably performed under reduced pressure, wherein the air pressure is 20mmHg (26.7 hPa) or less. Lamination may be performed by batch or continuous using a roll.
The vacuum lamination process can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nikko-materials, vacuum laminators manufactured by Kagaku Co., ltd., roll dry coaters manufactured by Hitachi Industries, and vacuum laminators manufactured by HITACHI AIC.
When the first composition layer 210 is formed using a resin sheet for coating having a support, the support is usually peeled off at an appropriate time before the step (III).
The first composition layer 210 formed on the substrate 300 in the step (I) generally contains a coating resin composition, preferably contains only the coating resin composition.
In the method for manufacturing an optical waveguide according to one embodiment of the present invention, step (II) of curing the first composition layer 210 is included after step (I). In this step (II), for example, the first composition layer 210 may be subjected to a heat treatment. The heat treatment conditions may be selected depending on the type and amount of the resin component in the coating fat composition, and are preferably in the range of 150 to 250℃and 20 to 180 minutes, more preferably in the range of 160 to 230℃and 30 to 120 minutes. The heat treatment is preferably performed in an inert atmosphere such as a nitrogen atmosphere.
In addition, the curing of the first composition layer 210 may be performed by an exposure process. In one example, the specific range of the exposure amount is preferably 10mJ/cm 2 or more, more preferably 50mJ/cm 2 or more, particularly preferably 200mJ/cm 2 or more, and is preferably 10,000mJ/cm 2 or less, more preferably 8,000mJ/cm 2 or less, further preferably 4,000mJ/cm 2 or less, particularly preferably 1,000mJ/cm 2 or less. In addition, the first composition layer 210 may be cured by a combination of exposure treatment and heat treatment.
Fig. 3 is a schematic cross-sectional view illustrating a step (II) of the optical waveguide manufacturing method according to an embodiment of the present invention. By curing the first composition layer 210 in step (II), as shown in fig. 3, a cured first composition layer 220 is obtained on the substrate 300. The cured first composition layer 220 forms a part of the clad layer 200, and is sometimes referred to as "lower clad layer" 220.
Fig. 4 is a schematic cross-sectional view illustrating a step (III) of the optical waveguide manufacturing method according to one embodiment of the present invention. In the method for manufacturing an optical waveguide according to one embodiment of the present invention, after the step (II), as shown in fig. 4, the step (III) of forming the second composition layer 110 containing the photosensitive resin composition of the present invention on the lower clad layer 220 as the cured first composition layer is included.
The method of forming the second composition layer 110 is not particularly limited. For example, the second composition layer 110 can be formed by coating the photosensitive resin composition of the present invention on the lower coating layer 220. From the viewpoint of smooth coating, a varnish-like photosensitive resin composition containing a solvent may be prepared and applied. The photosensitive resin composition of the present invention can be applied in the same manner as the coating resin composition. After the photosensitive resin composition of the present invention is applied, the second composition layer 110 may be dried as needed. The drying of the second composition layer 110 may employ the same method and conditions as the drying of the first composition layer 210.
The formation of the second composition layer 110 may be performed using, for example, a resin sheet. In specific examples, the photosensitive resin composition layer of the resin sheet is laminated on the lower coating layer 220, whereby the second composition layer 110 can be formed on the lower coating layer 220. Lamination of the resin sheets may be performed in the same manner as lamination of the resin sheets for coating. The support of the resin sheet is peeled off at an appropriate timing before the step (V).
The second composition layer 110 formed on the lower cladding layer 220 in the step (III) generally contains the photosensitive resin composition of the present invention, preferably contains only the photosensitive resin composition of the present invention.
Fig. 5 is a schematic cross-sectional view illustrating a step (IV) of a method for manufacturing an optical waveguide according to an embodiment of the present invention. In the method for manufacturing an optical waveguide according to an embodiment of the present invention, as shown in fig. 5, after the step (III), the step (IV) of exposing the second composition layer 110 to light is included.
In the step (V), a latent image is formed on the second composition layer 110 by exposure treatment. Specifically, in the exposure process, light P is selectively irradiated to a specific portion of the second composition layer 110. Thus, when the exposure treatment is performed, an exposure portion 111 that irradiates light and a non-exposure portion 112 that does not irradiate light are provided on the second composition layer 110. In general, the core resin composition functions as a negative photosensitive resin composition, and thus a latent image corresponding to the core layer is formed by the exposure portion 111.
From the viewpoint of performing selective exposure, the exposure process in the step (V) is generally performed using the mask 400. Specifically, in the exposure process, the second composition layer 110 is irradiated with light P through the mask 400 including the light transmitting portion 410 and the 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 thus cannot enter the non-exposure portion 112. Thus, the second composition layer 110 can be provided with the exposure portion 111 and the non-exposure portion 112 corresponding to the light transmitting portion 410 and the light shielding portion 420. As shown in fig. 5, the mask 400 may be adhered to the second composition layer 110 (contact exposure method), or may be exposed using parallel light rays (non-contact exposure method) without adhesion.
In general, 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. Thus, the light shielding portion 420 of the mask 400 is formed to have a planar shape corresponding to a portion of the optical waveguide where the core layer is absent. The "planar shape" refers to a shape as viewed from the thickness direction unless otherwise specified. Hereinafter, the light transmitting portion 410 formed in a planar shape corresponding to the core layer is sometimes referred to as a "mask pattern".
As the light P used in the exposure treatment in the step (V), an appropriate active light ray suitable for the composition of the photosensitive resin composition of the present invention is preferably used. The wavelength of the active light is usually 190nm to 1000nm, preferably 240nm to 550nm, and light having other wavelengths may be used. Specific examples of the active light source include ultraviolet rays, visible rays, electron rays, X-rays, and the like, and ultraviolet rays are particularly preferred. The exposure amount of the light P is preferably set so that a desired core layer can be formed after the curing in the step (VII). In one example, the specific range of the exposure amount in the step (V) is preferably 10mJ/cm 2 or more, more preferably 50mJ/cm 2 or more, particularly preferably 200mJ/cm 2 or more, preferably 10,000mJ/cm 2 or less, more preferably 8,000mJ/cm 2 or less, further preferably 4,000mJ/cm 2 or less, particularly preferably 1,000mJ/cm 2 or less.
In the case of forming the second composition layer 110 using the resin sheet of the present invention, a support (not shown) may be present on the second composition layer 110 in the step (IV). When a support is present on the second composition layer 110, exposure may be performed through the support, or exposure may be performed after the support is peeled off.
Since the photosensitive resin composition of the present invention functions as a negative photosensitive resin composition, the solubility of the exposed portion 111 in a developer is reduced. On the other hand, the non-exposed portion 112 has high solubility in a developer. The difference in solubility between the exposed portion 111 and the non-exposed portion 112 is used to perform development processing in the subsequent step (VI).
In the method for manufacturing an optical waveguide according to one embodiment of the present invention, the method may include a step (IX) of heating the second composition layer 110 from the viewpoint of curing the second composition layer 110 after the step (IV) and before the step (V). By the step (IX), the solubility of the exposure portion 111 in the developer can be rapidly reduced. The heating in the step (IX) may be performed by using a heating plate or by using an oven. The heating temperature may be, for example, 40 ℃ or more and 110 ℃ or less. The heating time may be, for example, 30 seconds to 60 minutes.
Fig. 6 is a schematic cross-sectional view illustrating a step (V) of a method for manufacturing an optical waveguide according to an embodiment of the present invention. In the method for manufacturing an optical waveguide according to one embodiment of the present invention, step (V) of developing the second composition layer 110 is included after step (IV). According to the development process, the latent image formed in the step (IV) can be developed. Since the photosensitive resin composition of the present invention functions as a negative photosensitive resin composition, the exposure portion 111 is not removed by the development process, but is removed not by the exposure portion 112 (see fig. 5), as shown in fig. 6. The exposed portion 111 of the second composition layer 110 remaining after development may have the same planar shape as the mask pattern of the light transmitting portion 410 (see fig. 5) of the mask 400 used in the step (IV).
As for the development method, a wet development method of bringing the second composition layer 110 into contact with a developer is generally performed. As the developer, an alkaline aqueous solution is generally used.
As the alkaline aqueous solution as the developer, for example, an aqueous solution of an alkali metal compound is mentioned. Examples of the alkali metal compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate. Examples of the basic aqueous solution include aqueous solutions of organic bases free of metal ions such as tetraalkylammonium hydroxide. The alkaline aqueous solution may be used alone or in combination of 1 or more than 2. Among them, from the viewpoint of significantly obtaining the effects of the present invention, alkali metal carbonates or bicarbonates are preferable, and sodium carbonate is more preferable.
In order to enhance the development effect, the developer may contain additives such as a surfactant and an antifoaming agent as needed.
The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but is preferably 20 ℃ or higher, preferably 50 ℃ or lower, more preferably 40 ℃ or lower.
Examples of the development method include a puddle method, a spray method, a dipping method, a brush coating method, a beat coating method, and an ultrasonic method. Among them, the spray method is suitable because it improves resolution. The spraying pressure in the case of using the spraying method is preferably 0.05MPa to 0.3MPa.
After development using the developer, the second composition layer 110 may be further rinsed. The rinsing is preferably performed using a solvent different from the developer. For example, the resin composition may be rinsed with a solvent or water of the same kind as those contained in the core resin composition. The rinsing time is preferably 5 seconds to 1 minute.
In addition, after development using a developer, a desmear treatment may be performed in order to remove the non-exposed portion which is not removed cleanly by the development. The desmear treatment may be performed according to various methods known to those skilled in the art for manufacturing a printed wiring board.
In the method for manufacturing an optical waveguide according to one embodiment of the present invention, step (VI) of curing the second composition layer 110 is included after step (V). The process (VI) generally includes heat treating the second composition layer 110. The heat treatment conditions can be selected according to the kind and amount of the resin component in the photosensitive resin composition of the present invention. For example, the heat treatment conditions in the step (VI) may be the same conditions as those of the heat treatment of the first composition layer 210 in the step (II).
Fig. 7 is a schematic cross-sectional view illustrating a step (VI) of a method for manufacturing an optical waveguide according to an embodiment of the present invention. By curing the second composition layer 110 in the step (VI), as shown in fig. 7, the core layer 100 as a cured second composition layer can be obtained on the lower clad layer 220.
Fig. 8 is a schematic cross-sectional view illustrating a step (VII) of the optical waveguide manufacturing method according to an embodiment of the present invention. In the method for manufacturing an optical waveguide according to one embodiment of the present invention, the step (VII) of forming a conductor layer on the core layer may be included after the step (VI) is completed and before the step (VIII). The conductor layer 500 formed on the core layer 100 is preferably formed by plating. In addition, before the conductor layer 500 is formed by plating, roughening treatment of the surface of the core layer 100 may be performed. Since the core layer 100 contains the photosensitive resin composition of the present invention, it has high resistance to the chemical solution used for the roughening treatment, and therefore the arithmetic average roughness (Ra) after the roughening treatment becomes small. Thereby, transmission loss can be reduced. Further, since the core layer 100 includes the photosensitive resin composition of the present invention, the peel strength between the core layer 100 and the conductor layer 500 can be improved even when the arithmetic average roughness (Ra) after roughening treatment is small.
The step and conditions of the roughening treatment are not particularly limited. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid.
Examples of the swelling liquid used in the roughening treatment include an alkali solution and a surfactant solution, and alkali solutions are preferable. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include: "SWELLING DIP securiganth P", "SWELLING DIP securiganth SBU" manufactured by America Japan, inc. The swelling treatment with the swelling liquid is not particularly limited, and may be performed by immersing the insulating layer in the swelling liquid at 30 to 90 ℃ for 1 to 20 minutes, for example. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.
Examples of the oxidizing agent used in the roughening treatment include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by ambett japan.
The neutralization solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by ambett japan. The treatment with the neutralizing solution may be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to impregnate the object subjected to roughening treatment with an oxidizing agent in a neutralization solution at 40 to 70 ℃ for 5 to 20 minutes.
As described above, the arithmetic average roughness Ra of the core layer surface after the roughening treatment is preferably 500nm or less, more preferably less than 400nm, further preferably 200nm or less, and still more preferably less than 200nm. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like.
After the roughening treatment is completed, a conductor layer 500 is formed on the roughened core layer 100. Specifically, the conductor layer 500 having a desired wiring pattern can be formed by plating the surface of the core layer 100 by a half-addition method, a full-addition method, or the like. From the viewpoint of ease of production, it is preferably formed by a half-addition method. An example of forming the conductor layer by the half-additive method is shown below.
A plating seed layer is formed by electroless plating on the surface of the core layer 100. Next, a mask pattern is formed on the formed plating seed layer, the mask pattern exposing a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby the conductor layer 500 having a desired wiring pattern can be formed.
Fig. 9 is a schematic cross-sectional view illustrating a step (VIII) of the optical waveguide manufacturing method according to one embodiment of the present invention. As shown in fig. 9, the method for manufacturing an optical waveguide according to an embodiment of the present invention includes a step (VIII) of forming a third composition layer 230 including a resin composition for a cladding layer on the core layer 100 and the conductor layer 500 after the step (VII). The third composition layer 230 is generally formed so as to cover the entirety of the outer peripheral surfaces of the core layer 100 and the conductor layer 500, which are not in contact with the lower cladding layer 220. Thus, the third composition layer 230 is formed in such a manner as to cover the core layer 100 and the conductor layer 500, and is also formed on the lower cladding layer 220.
The method of forming the third composition layer 230 is not particularly limited. For example, the third composition layer 230 may be formed by coating the resin composition for cladding on the core layer 100 and the conductor layer 500 (and on the lower cladding layer 220 as needed). The coating of the coating resin composition for forming the third composition layer 230 may be performed in the same manner as the coating of the coating resin composition for forming the first composition layer 210. After the coating resin composition is applied, the third composition layer 230 may be dried as needed. The drying of the third composition layer 230 may employ the same method and conditions as the drying of the first composition layer 210.
The third composition layer 230 may be formed using, for example, a resin sheet for coating. Specifically, the photosensitive resin composition layer of the coating resin sheet is laminated on the core layer 100 and the conductor layer 500 (and on the lower coating layer 220 as needed), whereby the third composition layer 230 can be formed on the core layer 100. Lamination of the resin sheet for cladding for forming the third composition layer 230 may be performed in the same manner as lamination of the resin sheet for cladding for forming the first composition layer 210. In the case where the third composition layer 230 is formed using a resin sheet for coating having a support, the support may be peeled off in any process.
In step (VIII), the third composition layer 230 formed on the core layer 100 and the conductor layer 500 generally contains a resin composition for a coating layer, preferably contains only a resin composition for a coating layer.
The method for manufacturing an optical waveguide according to one embodiment of the present invention includes a step (IX) of curing the third composition layer 230 after the step (VIII). The curing of the third resin composition layer 230 in this step (IX) may be generally performed in the same manner as the curing of the first composition layer 210.
Fig. 10 is a schematic cross-sectional view illustrating a process (IX) of a method for manufacturing an optical waveguide according to an embodiment of the present invention. By curing the third composition layer 230 in step (IX), a cured third composition layer 240 is obtained on the core layer 100 as shown in fig. 10. The cured third composition layer 240 forms a part of the clad layer 200 and is sometimes referred to as an "upper clad layer" 240. The upper cladding layer 240 and the lower cladding layer 220 form the cladding layer 200. Accordingly, the optical waveguide 10 including the clad layer 200 including the lower clad layer 220 and the upper clad layer 240 and the core layer 100 provided in the clad layer 200 can be obtained.
The method for manufacturing the optical waveguide 10 may further include any step in combination with the above steps.
The method of manufacturing the optical waveguide 10 may include, for example, a step of forming a protective layer (not shown). The method for manufacturing the optical waveguide 10 may include, for example, a step of cutting the manufactured optical waveguide 10.
The above-described steps may be repeated for the method of manufacturing the optical waveguide 10. For example, the steps (I) to (IX) may be repeated to produce an optical waveguide having a multilayer structure in which a core layer and a cladding layer are alternately provided on the substrate 300 in the thickness direction.
[ Photoelectric hybrid substrate ]
An opto-electronic hybrid board according to an embodiment of the present invention includes the optical waveguide. In general, an opto-electronic hybrid board includes an optical waveguide and a circuit board. The circuit board may include an electronic component and a wiring connected to the electronic component. Examples of the electronic component include passive components such as a capacitor, an inductor, and a resistor; active components such as semiconductor chips. The optical waveguide and the wiring of the circuit board may be connected via the photoelectric conversion element. The photoelectric conversion element may include a light emitting element (for example, a surface light emitting diode) capable of converting electricity into light and a light receiving element (for example, a photodiode) capable of converting light into electricity in combination. The opto-electric hybrid board may further include an optical element such as a mirror for adjusting the optical path.
A preferred example of the opto-electric hybrid board is a board having a chip obtained by forming an optical integrated circuit on a silicon wafer. Early practical use of the chip using silicon photoelectrons is expected, and it is expected to be mounted on, for example, a semiconductor package. The opto-electric hybrid board provided with the chip includes, for example, a circuit board, a chip mounted on the circuit board, and an optical waveguide. The optical waveguide may be used to connect wiring of a circuit substrate with a chip or to connect between a plurality of chips.
In chips manufactured by silicon photoelectrons, light having wavelengths of 1310nm and 1550nm is often used, and particularly 1310nm is the main stream (Ji Tianxiang, a large auxiliary of pipe, dan Chongming, "single-mode polymer waveguide manufacturing by Mosquito method and low loss (Mosquito, よ, a line of space, a low loss of space), the 28 th electronic installation society, the spring lecture university, 2014). Accordingly, the optical waveguide is preferably capable of transmitting light at wavelengths of 1310nm and 1550nm or close thereto, and preferably capable of transmitting light at wavelengths of 1300nm to 1320nm, for example. According to the optical waveguide of the above embodiment, light of these wavelengths can be transmitted.
In general, with respect to single mode and multimode, single mode enables faster transmission. Therefore, from the viewpoint of high-speed transmission, a single-mode optical waveguide is preferable as an optical waveguide applied to an opto-electronic hybrid circuit. In the single mode optical waveguide, the width of the core layer is preferably small. For example, it is preferable to form the core layer to have a width of 10 μm or less or 5 μm or less. In addition, when the optical waveguide is applied to a semiconductor package, it is preferable that the optical waveguide has a core layer having a small width from the viewpoint of improving the degree of freedom in designing the package. According to the optical waveguide of the above embodiment, the width of the core layer can be reduced as described above.
On the other hand, when a plurality of opto-electric hybrid boards are connected, these boards may be connected by optical fibers. For example, a plurality of photoelectric hybrid substrates may be provided on a holder, and these photoelectric hybrid substrates may be connected to each other via optical fibers. The mainstream of the optical fiber connecting substrates in this way is multimode. Accordingly, from the viewpoint of being connectable to the optical fiber, a multimode optical waveguide may be used as the optical waveguide provided on the opto-electronic hybrid board.
From the viewpoint of improving versatility, it is desirable that the optical waveguide is applicable to both single mode and multimode. Further, it is desirable to reduce the minimum width of the core layer of these optical waveguides and to improve the degree of freedom of the line width of the core layer. According to the optical waveguide of the above embodiment, by using the photosensitive resin composition of the present invention in the core, a fine core can be formed and the occurrence of surface irregularities of the core can be suppressed, so that the minimum width of the core layer can be reduced. In addition, according to the optical waveguide of the above embodiment, any of single-mode and multi-mode optical waveguides can be obtained. Thus, the optical waveguide described in the above embodiments can be applied to a wide range. Further, the optical waveguide according to the above embodiment is suitable for use in an opto-electronic hybrid board, since the optical waveguide can be applied in a wide range and can suppress the transmission loss of light.
Examples
The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts refer to "parts by mass" and "% by mass", respectively, unless otherwise specified. The operations described below were performed in the atmosphere at normal temperature and normal pressure (23 ℃ C., 1 atm), unless otherwise specified.
Synthesis example 1: synthesis of resins containing carboxyl groups and olefinic double bonds
325 Parts of an epoxy resin having a naphthol aralkyl skeleton (ESN-475V, manufactured by Nikko Chemicals Co., ltd.) having an epoxy equivalent of 325g/eq was charged into a flask equipped with a gas introducing pipe, a stirring device, a condenser and a thermometer, 340 parts of carbitol acetate was added and dissolved by heating, and 0.46 part of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated to 95 to 105℃and 72 parts of acrylic acid was slowly added dropwise thereto to react for 16 hours. The reaction product was cooled to 80 to 90℃and 80 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was allowed to react for 8 hours and cooled. The amount of the solvent was adjusted to obtain a resin solution (nonvolatile matter: 70%) having an acid value of 60mgKOH/g as a solid. The weight average molecular weight was 1000.
< Production example 1: production of coating resin composition
25 Parts of the ester-modified epoxy acrylate resin having a naphthol aralkyl skeleton (nonvolatile content: 70%) obtained in Synthesis example 1, 12 parts of a naphthalene skeleton epoxy resin (HP-4710, manufactured by DIC Co., ltd., "Omnirad 379EG", manufactured by IGM Co., ltd.), 1.5 parts of a photopolymerization initiator (DPHA, dipentaerythritol hexaacrylate, manufactured by Japanese chemical Co., ltd.), 13 parts of a reactive diluent (DPHA, dipentaerythritol hexaacrylate, manufactured by Japanese chemical Co., ltd.), 30 parts of spherical silica surface-treated with an aminosilane coupling agent (180 nmSX-C1, manufactured by Yakuma Co., ltd., specific surface area: 20m 2/g, average particle diameter: 0.2 μm), and 10 parts of methyl ethyl ketone were mixed, and a varnish-like resin composition was prepared using a high-speed rotary mixer.
< Example 1: production of photosensitive resin composition
26 Parts of the ester acid-modified epoxy acrylate resin having a naphthol aralkyl skeleton (nonvolatile content: 70%) obtained in Synthesis example 1, 12 parts of the naphthalene skeleton epoxy resin (HP-4710, manufactured by DIC Co., ltd., "Omnirad 379EG", manufactured by IGM Co., ltd.), 1.5 parts of the photo-polymerization initiator (Omnirad 379EG ", manufactured by Co., ltd.), 0.5 part of the non-developable polymer (acrylic polymer" POLYFLOW WS-314", manufactured by Co., ltd.), 11.5 (cal/cm 3)1/2, molecular weight: 2 ten thousand), 13 parts of the reactive diluent (DPHA, manufactured by Japanese chemical Co., ltd.," dipentaerythritol hexaacrylate "), and 10 parts of methyl ethyl ketone were mixed together, and a varnish-like resin composition was prepared by using a high-speed rotary mixer.
< Examples 2 to 12, comparative examples 1 to 2: production of photosensitive resin composition
A varnish-like photosensitive resin composition was prepared in the same manner as in example 1, except that the components were mixed according to the compounding compositions shown in the following table. In the table, the amount of each component is referred to as a mass part, and indicates an actual amount to be used.
TABLE 1
。
The shorthand in the table, etc., is as follows:
(A) Composition of the components
HP-4710: naphthalene type tetrafunctional epoxy resin (HP-4710, manufactured by DIC Co., ltd., "170 g/eq epoxy equivalent.)
ESN-475V: naphthol aralkyl skeleton epoxy resin (ESN-475V, manufactured by Nissan chemical materials Co., ltd., epoxy equivalent weight of about 330 g/eq.)
NC3000H: biphenyl type epoxy resin (NC 3000H, manufactured by Japanese chemical Co., ltd., epoxy equivalent of 290 g/eq.)
850: Bisphenol A type epoxy resin (EPICLON/850 from DIC Co., ltd.; about 183-193 g/eq in epoxy equivalent.)
(B) Composition of the components
Synthesis example 1: the resin having carboxyl groups and olefinic double bonds synthesized in Synthesis example 1 had a nonvolatile content of 70%
CCR-1171H: (Japanese chemical Co., ltd. "CCR-1171H", which contains a cresol novolak skeleton, an acid value of 99mgKOH/g, a nonvolatile matter content of 60%, a solvent PGMEA, a molecular weight of 7500, and an SP value of 9.5 (cal/cm 3)1/2)
ZCR-1761H: (ZCR-1761H, manufactured by Japanese chemical Co., ltd., containing a biphenyl skeleton, an acid value of 60mgKOH/g, a nonvolatile matter content of 70%, a solvent PGMEA, a molecular weight of 3000, and an SP value of 9.9 (cal/cm 3)1/2)
(C1) Composition of the components
Omnirad 379EG: compounds of the following structure (manufactured by IGM Co., ltd., molecular weight 380.5, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) -butan-1-one, CAS 119344-86-4)
[ Chemical formula 11]
Irgacure OXE-02: a compound of the following structure (manufactured by BASF corporation, molecular weight 412.5,1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime)
[ Chemical formula 12]
(C2) Composition of the components
Omnirad 819: a compound of the following structure (manufactured by IGM Co., ltd., molecular weight 418.5, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide)
[ Chemical formula 13]
(D) Composition of the components
WS-314: acrylic Polymer (POLYFLOW WS-314, co., ltd., SP value: 11.5 (cal/cm 3)1/2, molecular weight 2 ten thousand)
No.99C: acrylic Polymer (POLYFLOW No.99C, co., ltd., SP value: 9.7 (cal/cm 3)1/2, molecular weight 8000)
(E) Composition of the components
Y50SZ-AM1: spherical silica surface-treated with an aminosilane coupling agent (Y50 SZ-AM1, manufactured by Yakema Co., ltd.), having a specific surface area of 60m 2/g, an average particle diameter of 0.05 μm, and a solid content of 50%
(F) Composition of the components
DPHA: dipentaerythritol hexaacrylate manufactured by Japanese chemical Co., ltd
(G) Composition of the components
MEK: methyl ethyl ketone
(H) Composition of the components
UT-1001: acrylic Polymer (ACTFLOW UT-1001, manufactured by comprehensive research chemical Co., ltd., "SP value: 8.6 (cal/cm 3)1/2, molecular weight 3500)
AC-2300C: polyolefin (product of Co., ltd. "FLOWLEN AC-2300C", SP value: 8.4 (cal/cm 3)1/2, molecular weight: 3500).
< Production of resin sheet >
Using the photosensitive resin compositions produced in examples 1 to 12 and comparative examples 1 to 3, a plurality of resin sheets having photosensitive resin composition layers with different thicknesses were produced by the following method.
As a support, a polyethylene terephthalate film (LumirrorT 6AM, manufactured by Toli Co., ltd., thickness of 38 μm, softening point of 130 ℃ C.) was prepared. The photosensitive resin compositions produced in production example 1, examples 1 to 12 and comparative examples 1 to 3 were uniformly applied to the support by a die coater so that the thickness of the dried photosensitive resin composition layer became 5 μm or 10 μm, and dried at 80℃to 110℃for 6 minutes to form a photosensitive resin composition layer. Next, a cover film (biaxially stretched polypropylene film, MA-411 made by prince F-TEX) was placed on the surface of the photosensitive resin composition layer, and laminated at 80 ℃.
As a support, a polyethylene terephthalate film (LumirrorT 6AM, manufactured by Toli Co., ltd., thickness of 38 μm, softening point of 130 ℃ C.) was prepared. The resin composition produced in production example 1 was uniformly coated with the dried resin composition layer having a thickness of 5 μm, 10 μm or 20 μm by a die coater, and dried at 80℃to 110℃for 6 minutes to form a photosensitive resin composition layer. Next, a cover film (biaxially stretched polypropylene film, MA-411 made by prince F-TEX) was placed on the surface of the photosensitive resin composition layer, and laminated at 80 ℃.
[ Evaluation of core Forming Property ]
(Evaluation of minimum thin line formation Width)
A copper layer of a glass epoxy substrate (copper-clad laminate) having a copper layer of 18 μm in thickness was roughened with a surface treatment agent (CZ 8100, manufactured by MEC corporation) containing an organic acid, to prepare a substrate. A resin sheet having a thickness of 5 μm was laminated on the previous substrate at 80℃to peel off the support, thereby forming a photosensitive resin composition layer, which was produced using the resin composition prepared in production example 1. Thereafter, ultraviolet exposure was performed using a projection exposure apparatus (manufactured by USHIO Motor Co., ltd. "UFX-2240") with an exposure energy of 8 steps, which is the number of steps of the gloss residual stage of the 41-step stage exposure meter. The quartz glass mask uses a mask without an exposure pattern. After standing at room temperature for 30 minutes, the support was peeled off. The entire surface of the photosensitive resin composition layer was subjected to spray development for 1 minute at a spray pressure of 0.2MPa with a1 mass% aqueous sodium carbonate solution at 30 ℃. After the spray development, ultraviolet irradiation of 2J/cm 2 was performed, and further, a heating treatment was performed at 170℃for 1 hour under a nitrogen atmosphere, whereby a lower layer clad layer was formed on the copper-clad laminate.
The cover film was peeled from a resin sheet having a photosensitive resin composition layer of 10 μm thickness produced using the photosensitive resin compositions produced in the examples and comparative examples. The resin sheet was placed on the lower clad layer so that the photosensitive resin composition layer of the resin sheet was in contact with the lower clad layer, and the resin sheet was laminated using a vacuum laminator (manufactured by Nikko-Materials corporation, "VP 160"), to form a photosensitive resin composition layer on the lower clad layer. The lamination conditions were set as follows: vacuum pumping time is 30 seconds, pressure connection temperature is 100 ℃, pressure connection pressure is 0.7MPa, and pressure connection time is 30 seconds. Thus, a laminate comprising the copper-clad laminate, the lower clad layer, and the resin sheet in this order was obtained. Thereafter, the support is peeled off to expose the photosensitive resin composition layer.
The photosensitive resin composition layer was exposed to ultraviolet light using a projection exposure apparatus (manufactured by USHIO motor company, "UFX-2240") with an exposure energy of 8 steps of the number of steps of gloss residual stage in a 41-step exposure meter. The exposure was performed using a quartz glass mask having a first mask pattern having an L/S (line width/line width) of 10 μm/10 μm and drawing a straight line, a second mask pattern having an L/S (line width/line width) of 5 μm/5 μm and drawing a straight line, and a third mask pattern having an L/S (line width/line width) of 3 μm/3 μm and drawing a straight line. After exposure, the support was peeled off after standing at room temperature for 30 minutes. For the entire surface of the photosensitive resin composition layer, a1 mass% aqueous sodium carbonate solution at 30 ℃ as a developer was subjected to spray development at a spray pressure of 0.2MPa for 1 minute. After spray development, ultraviolet irradiation of 2J/cm 2 was performed, and further, heat treatment was performed at 170 ℃ for 1 hour under a nitrogen atmosphere, whereby a sample comprising a copper-clad laminate, an underlying clad layer, and a wire layer (layer formed of a cured product of a resin composition) in this order was obtained.
The obtained sample was observed with a Scanning Electron Microscope (SEM) (magnification was 2000 times), and the minimum thin line formation width (the width of the line layer having the smallest width among the line layers that can be formed) was measured. The aspect ratio is calculated by dividing the thickness of the wire layer by the minimum thin wire formation width. The minimum thin line formation width in the core formability was evaluated according to the following criteria. Line width represents the width of the line layer;
o: the aspect ratio of all the line layers having a line width of 10 μm or less is 0.8 or more
Delta: the aspect ratio of all the line layers having a line width of 10 μm or less is 0.6 or more and less than 0.8
X: the aspect ratio of at least one of the line layers having a line width of 10 μm or less is less than 0.6.
[ Measurement of optical Transmission loss ]
(1-1. Formation of lower cladding layer)
The cover film was peeled from a resin sheet having a photosensitive resin composition layer of 10 μm thickness produced using the resin composition produced in production example 1. A resin sheet was placed on a 4-inch silicon wafer so that the photosensitive resin composition layer was in contact with the silicon wafer, and the resin sheet was laminated using a vacuum laminator (VP 160, manufactured by Nikko-Materials). The lamination conditions were set as follows: vacuum pumping time is 30 seconds, pressure connection temperature is 100 ℃, pressure connection pressure is 0.7MPa, and pressure connection time is 30 seconds. Thereafter, the support was peeled off to obtain an intermediate laminate I including a silicon wafer and a photosensitive resin composition layer.
The photosensitive resin composition layer of the intermediate laminate I was subjected to ultraviolet exposure using a projection exposure apparatus (usaio motor company "UFX-2240") with an exposure energy of 8 steps of the number of steps of gloss residual stage of the 41-step exposure meter. After exposure, ultraviolet irradiation of 2J/cm 2 was performed. The intermediate laminate I was put into a cleaning oven, heated from room temperature to 170 ℃, and after reaching 170 ℃, heat treatment was performed under a nitrogen atmosphere for 60 minutes to cure the photosensitive resin composition layer. The lower clad layer was formed by curing the photosensitive resin composition layer, and an intermediate laminate II including a silicon wafer and the lower clad layer was obtained.
(1-2. Formation of core layer)
The cover film was peeled from a resin sheet having a photosensitive resin composition layer of 5 μm thickness produced using the photosensitive resin compositions produced in examples and comparative examples. A resin sheet was placed on the surface of the lower clad layer of the intermediate laminate II so that the photosensitive resin composition layer was in contact with the lower clad layer, and the laminate was laminated using a vacuum laminator (VP 160, manufactured by Nikko-Materials). The lamination conditions were set as follows: vacuum pumping time is 30 seconds, pressure connection temperature is 100 ℃, pressure connection pressure is 0.7MPa, and pressure connection time is 30 seconds. Thereafter, the support was peeled off to obtain an intermediate laminate III comprising a silicon wafer, a base coating layer, and a photosensitive resin composition layer in this order.
The photosensitive resin composition layer of the intermediate laminate III was subjected to ultraviolet exposure using a projection exposure apparatus (usaio motor company "UFX-2240") with an exposure energy of 8 steps of the number of steps of gloss residual stage of the 41-step exposure meter. The exposure was performed using a quartz glass mask having a mask pattern of L/S (line width/line width) of 5 μm/100 μm capable of drawing a plurality of straight lines of 1cm in length, a mask pattern of L/S (line width/line width) of 5 μm/100 μm capable of drawing a plurality of straight lines of 2cm in length, and a mask pattern of L/S (line width/line width) of 5 μm/100 μm capable of drawing a plurality of straight lines of 3cm in length. In the L/S of the quartz glass mask, the line width corresponds to the width of the core layer, and the line pitch corresponds to the interval between the core layers. After exposure, the support was peeled off after standing at room temperature for 30 minutes. The entire surface of the photosensitive resin composition layer was subjected to spray development for 1 minute at a spray pressure of 0.2MPa with a1 mass% aqueous sodium carbonate solution at 30 ℃. After spray development, ultraviolet irradiation of 2J/cm 2 was performed. Thereafter, the intermediate laminate III was put into a clean oven, heated from room temperature to 170 ℃, and after reaching 170 ℃, heat treatment was performed under a nitrogen atmosphere for 60 minutes to cure the photosensitive resin composition layer.
The core layer is formed by curing the photosensitive resin composition layer, and an intermediate laminate IV including a silicon wafer, an underlying clad layer, and a core layer in this order is obtained.
(1-3. Formation of upper coating layer)
The cover film was peeled from a resin sheet having a photosensitive resin composition layer of 20 μm thickness produced using the resin composition produced in production example 1. A resin sheet was placed on the core layer of the intermediate laminate IV so that the photosensitive resin composition layer was in contact with the core layer, and the laminate was laminated using a vacuum laminator (manufactured by Nikko-Materials corporation, "VP 160"). The lamination conditions were set as follows: vacuum pumping time is 30 seconds, pressure connection temperature is 100 ℃, pressure connection pressure is 0.7MPa, and pressure connection time is 30 seconds. Thereafter, the support was peeled off to obtain an intermediate laminate V comprising, in order, a silicon wafer, an underlying coating layer, a core layer, and a photosensitive resin composition layer.
The photosensitive resin composition layer of the intermediate laminate V was subjected to ultraviolet exposure using a projection exposure apparatus (usaio motor company "UFX-2240") with an exposure energy of 8 steps of the number of steps of gloss residual stage of the 41-step exposure meter. After exposure, ultraviolet irradiation of 2J/cm 2 was performed. The intermediate laminate V was put into a cleaning oven, heated from room temperature to 170 ℃, and after reaching 170 ℃, heat treatment was performed under a nitrogen atmosphere for 60 minutes to cure the photosensitive resin composition layer. The upper layer coating layer was formed by curing the photosensitive resin composition layer, and a sample laminate including a silicon wafer, a lower layer coating layer, a core layer, and an upper layer coating layer in this order was obtained.
In the sample laminate, the combination of the lower coating layer and the upper coating layer forms the coating layer. Thus, an optical waveguide including the clad layer and the core layer present in the clad layer is obtained. In the sample laminate, the core layer corresponds to a mask pattern of the quartz glass mask, and has linear patterns having lengths of 1cm, 2cm, and 3cm, and the width (line width) and the pitch (line pitch) of the core layer included in these patterns match the width (line width) and the pitch (line pitch) of the mask pattern.
[ Evaluation of optical waveguide ]
(Measurement of optical Transmission loss of correction optical System)
The transmission loss of an optical system having a structure in which the test substrate and the light collecting module were removed from the optical system for measuring transmission loss of the test substrate described later was measured. That is, a light source (1310 nm light source, THORLABS company "LPSC-1310-FC") and a light receiver (Keysight company optical power meter "N7742") were connected via an optical fiber (incident optical fiber) by using a vibration isolation table covered with a black curtain, and an optical system for calibration was obtained. The light source is made to emit light, the intensity of the light entering the light receiver is measured by the light receiver, and the loss of the optical system for correction is measured.
(Preparation of test substrate)
From the sample laminate produced using the photosensitive resin compositions of examples and comparative examples, the core layer and the surrounding clad layer were cut at the portion where the core layer was formed, and a test substrate having an optical transmission path was obtained.
(Measurement of optical Transmission loss)
A test substrate was placed on a vibration isolation table covered with a black window shade. A light collecting module (opening number: 0.18) was connected to one end (incident end) of the optical waveguide of the test substrate, and the light collecting module was connected to a light source (1310 nm light source, THORLABS, LPSC-1310-FC) via an optical fiber (incident optical fiber). The other end (emission end) of the optical waveguide of the test substrate was connected to another light collecting module (opening number: 0.18), and the light collecting module was connected to a light receiver (optical power meter "N7742" manufactured by Keysight corporation) via an optical fiber (emission optical fiber). Through the above operation, the light emitted from the light source is transmitted through the optical fiber (incident optical fiber), the light collecting module, the optical waveguide, the light collecting module, and the optical fiber (outgoing optical fiber) in this order, and then the optical system entering the light receiver is obtained. Hereinafter, this optical system may be referred to as a sample optical system. The light source is made to emit light, and the intensity of the light entering the light receiver is measured by the light receiver, and the loss of the sample optical system is measured.
The loss of the optical waveguide included in the test substrate was obtained by subtracting the loss of the optical system for correction from the loss of the sample optical system.
(Measurement of transmission loss (dB/cm) of optical waveguide)
The loss of each of the optical waveguide was measured for an optical waveguide having a length of 1cm, an optical waveguide having a length of 2cm, and an optical waveguide having a length of 3 cm. The measurement result is plotted on a coordinate system having the length of the optical waveguide as the horizontal axis and the loss of the optical waveguide as the vertical axis, and a three-point coordinate system showing the measurement result is obtained. The three-point approximate straight line is calculated by the least square method, and the slope of the approximate straight line is obtained as the loss (transmission loss) per unit distance of the optical waveguide, and evaluated according to the following criteria:
and (3) the following materials: the optical transmission loss is less than 0.5dB/cm
O: the optical transmission loss is more than 0.5dB/cm and less than 1.0dB/cm
Delta: the optical transmission loss is more than 1.0dB/cm and less than 2.0dB/cm
X: the optical transmission loss is more than 2.0 dB/cm.
(Confirmation of mode)
The photoreceiver is removed and instead an infrared camera (InGaAs camera, with 100-fold objective) is provided. The light source is made to emit light, and the light emitted from the end of the optical fiber (exit optical fiber) is captured by an infrared camera. When only one right circular light edge is observed, it is determined as a single mode. In addition, when a plurality of edges are observed, it is determined that multimode is present. In the table, "S" represents a single mode and "M" represents a multiple mode.
[ Measurement of absorbance of solution of photosensitive resin composition ]
Solutions of the photosensitive resin compositions produced in examples and comparative examples were prepared, and the absorbance of the solutions was measured by the following method. That is, a mixed solvent of MEK (methyl ethyl ketone) and cyclopentanone (MEK: pentanone=1:1) was mixed into the photosensitive resin compositions produced in examples and comparative examples, and a photosensitive resin composition solution having a concentration of 20 mass% was prepared. The solution was placed in a 1cm quartz cuvette, and absorbance Abs at a wavelength of 1310nm was measured by an ultraviolet-visible near infrared spectrophotometer (manufactured by japan spectroscopy, V-770), and evaluated according to the following criteria:
and (3) the following materials: absorbance of less than 0.0025
O: absorbance of 0.0025 or more and less than 0.0050
Delta: absorbance of 0.0050 or more and less than 0.0100
X: the absorbance is 0.0100 or more.
< Evaluation of arithmetic average roughness and peel Strength (peel Strength) of copper-plated conductor layer >
(Production of evaluation laminate A and sample A)
Roughening was performed on a copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit having a thickness of 18 μm was formed by patterning the copper layer by using a surface treatment agent (CZ 8100, manufactured by MEC corporation) containing an organic acid. Next, a prefabricated resin sheet was placed so that the photosensitive resin composition layer was in contact with the copper circuit surface, and laminated using a vacuum laminator (manufactured by Nikko-materials company, VP 160), to produce a laminate a for evaluation in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The crimping conditions were set as: the vacuum time is 30 seconds, the pressure welding temperature is 80 ℃, the pressure welding pressure is 0.7MPa, and the pressurizing time is 30 seconds. After the laminate A for evaluation was produced, it was allowed to stand at room temperature (25 ℃) for 30 minutes or longer.
Using a patterning device, ultraviolet exposure was performed from the support of the laminate a for evaluation using an exposure energy of 8 steps of the number of steps of gloss remaining in the 41-step exposure meter. The quartz glass mask uses a mask without an exposure pattern. After standing at room temperature for 30 minutes, the support was peeled off from the laminate sheet for evaluation a. The entire surface of the photosensitive resin composition layer on the evaluation laminate a was subjected to spray development for 1 minute at a spray pressure of 0.2MPa with a 1 mass% aqueous sodium carbonate solution at 30 ℃. After the spray development, ultraviolet irradiation was performed at 2J/cm 2, and further, a heating treatment was performed at 170℃for 1 hour to cure the photosensitive resin composition layer.
The laminate A for evaluation was immersed in SWELLING DIP Securiganth P containing diethylene glycol monobutyl ether (manufactured by America Japan Co., ltd.) as a swelling liquid at 60℃for 10 minutes, then immersed in Concentrate Compact P (KMnO 4:60 g/L, naOH:40g/L aqueous solution) manufactured by America Japan Co., ltd.) as a roughening liquid at 80℃for 10 minutes, and finally immersed in Reduction Solution Securiganth P manufactured by America Japan Co., ltd., as a neutralization liquid at 40℃for 5 minutes. The laminated sheet after the roughening treatment was used as sample a.
(Evaluation of arithmetic average roughness (Ra))
For sample A, a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co.) was used, and the arithmetic average roughness (Ra) was obtained from the obtained values by setting the measurement range to 121. Mu.m.times.92. Mu.m using a VSI mode and a 50-fold lens. Then, the average value of 10 points was obtained as a measurement value, and the measurement value was evaluated according to the following criteria:
o: arithmetic average roughness less than 200nm
Delta: an arithmetic average roughness of 200nm to 400nm
X: the arithmetic average roughness is greater than 400nm.
(Evaluation of peel strength (peel strength) of copper-plated conductor layer)
In order to form a circuit on the surface of the insulating layer, sample a was immersed in an electroless plating solution containing PdCl 2, followed by immersion in an electroless copper plating solution. After annealing by heating at 150℃for 30 minutes, a resist was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25. Mu.m. Next, an annealing treatment was performed at 180℃for 60 minutes. The sample thus obtained was designated as sample B.
The conductor layer of sample B was cut at a portion having a width of 10mm and a length of 100mm, one end thereof was peeled off and held by a jig (model AUTO COM test machine, AC-50C-SL, manufactured by TSE Co.) and the load (kgf/cm) at a speed of 50 mm/min at 35mm in the vertical direction was measured at room temperature, and the evaluation was made on the basis of the following criteria:
o: peel strength of 0.3kgf/cm or more
Delta: the peel strength is less than 0.3kgf/cm and is more than 0.2kgf/cm
X: the peel strength is less than 0.2kgf/cm.
TABLE 2
。
Description of the reference numerals
10. Optical waveguide
100. Core layer
110. A second composition layer
111. Exposure part
112. Non-exposure part
200. Coating layer
210. A first composition layer
220. Cured first composition layer (lower coating)
230. Third composition layer
240. A cured third composition layer (upper cladding layer)
300. Substrate material
400. Mask for mask
410. Light transmitting part
420. Light shielding part
500. And a conductor layer.

Claims (14)

1. A photosensitive resin composition comprising:
(A) An epoxy resin,
(B) A resin containing carboxyl groups and olefinic double bonds,
(C) Photopolymerization initiator
(D) A non-developable polymer having a solubility parameter (SP value) of 9 (cal/cm 3)1/2 or more and 13 (cal/cm 3)1/2 or less).
2. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the component (D) is 3000 or more and 100000 or less.
3. The photosensitive resin composition according to claim 1, wherein component (D) comprises an acrylic polymer.
4. The photosensitive resin composition according to claim 1, wherein the component (D) has a structural unit represented by the following formula (D-1) and a structural unit represented by the formula (D-2):
In the formula (D-1), R 1 independently represents a hydrogen atom or a methyl group, R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, p independently represents an integer of 2 to 4, q represents an integer of 2 to 100,
In the formula (D-2), R 3 independently represents a hydrogen atom or a methyl group, and R 4 independently represents an alkyl group having 1 to 22 carbon atoms.
5. The photosensitive resin composition according to claim 1, wherein the solubility parameter (SP value) of component (B) is 9 (cal/cm 3)1/2 or more and 11 (cal/cm 3)1/2 or less).
6. The photosensitive resin composition according to claim 1, further comprising (E) an inorganic filler having an average particle diameter of 100nm or less.
7. The photosensitive resin composition according to claim 1, which is used for producing a core layer of an optical waveguide.
8. A resin sheet comprising a support and a photosensitive resin composition layer formed on the support,
The photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7.
9. The resin sheet according to claim 8, wherein the photosensitive resin composition layer has a thickness of 1 μm or more and 15 μm or less.
10. A photosensitive resin composition kit comprising a core photosensitive resin composition and a coating resin composition, wherein the core photosensitive resin composition comprises the photosensitive resin composition according to any one of claims 1 to 7.
11. An optical waveguide having a core layer and a cladding layer,
The core layer comprises a cured product of the photosensitive resin composition according to any one of claims 1 to 7.
12. The optical waveguide of claim 11, capable of transmitting light having a wavelength of 1300nm to 1320 nm.
13. The optical waveguide of claim 12, which is a single mode optical waveguide.
14. An opto-electronic hybrid board comprising the optical waveguide according to claim 13.
CN202311407587.3A 2022-11-01 2023-10-27 Photosensitive resin composition Pending CN117991587A (en)

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