CN114253075A - Photosensitive resin composition for ink jet - Google Patents
Photosensitive resin composition for ink jet Download PDFInfo
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- CN114253075A CN114253075A CN202111105516.9A CN202111105516A CN114253075A CN 114253075 A CN114253075 A CN 114253075A CN 202111105516 A CN202111105516 A CN 202111105516A CN 114253075 A CN114253075 A CN 114253075A
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- acrylic compound
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The invention provides a photosensitive resin composition for ink jet, which can form a cured product with excellent coating performance, flame retardance and gold plating resistance for ink jet without damaging basic characteristics such as adhesion and electrical insulation of a substrate with a circuit pattern. The photosensitive resin composition for ink jet contains (A) a (methyl) acrylic compound with the weight-average molecular weight of more than 500, (B) a (methyl) acrylic compound with the weight-average molecular weight of less than 500, (C) a phosphorus-containing flame retardant, (D) an amine modified (methyl) acrylic compound and (E) a photopolymerization initiator, wherein the (C) phosphorus-containing flame retardant has a functional group which is cured by active energy rays, and the (D) amine modified (methyl) acrylic compound has a functional group which is cured by active energy rays.
Description
Technical Field
The present invention relates to a photosensitive resin composition which can be applied to a substrate such as a printed wiring board using a rigid substrate or a flexible substrate by an ink jet method and has flame retardancy.
Background
Conventionally, when an insulating coating is formed on a substrate having a desired circuit pattern (for example, a printed wiring board), a photosensitive resin composition is applied by a screen printing method or the like, and then predryed, a negative film having a pattern that allows light to pass through other than pads of the circuit pattern is bonded to the applied photosensitive resin composition, and active energy rays such as ultraviolet rays are irradiated from above, and a non-exposed region corresponding to the pad is removed by an alkaline aqueous solution, whereby a coating film of the photosensitive resin composition is developed and heat-cured (post-treatment).
However, the method of forming the insulating coating on the substrate involves many processing steps such as development, which makes the operation complicated. Therefore, in recent years, the following is also performed: a photosensitive resin composition is ejected to a substrate having a desired circuit pattern by an ink jet method to form a coating film, and a curing treatment of exposure to active energy rays such as laser light and ultraviolet light is performed on the coating film to form a cured coating film, and the cured coating film is further subjected to a heat curing treatment to form an insulating coating having a desired pattern.
As a curable resin composition suitable for the production of a printed wiring board and used in an ink jet method, for example, a curable resin composition containing a bisallylnadiimide (Bisallylnadic Imide) compound having a predetermined chemical structure, a bismaleimide compound having a predetermined chemical structure, and a diluent and having a viscosity of 150mPa · s or less at 25 ℃.
On the other hand, since a heat generating element such as an electronic element is mounted on a printed wiring board, flame retardancy is sometimes required for a cured coating film of a photosensitive resin composition for forming an insulating coating. In order to stably discharge a photosensitive resin composition having flame retardancy by an ink jet method, it is necessary to blend a flame retardant having a small particle diameter, for example, an average particle diameter of 1 μ or less, into the photosensitive resin composition. Therefore, in order to apply a photosensitive resin composition by an ink jet method, a powdery flame retardant may be mixed in the photosensitive resin composition and pulverized.
However, even if the powdery flame retardant is subjected to the pulverization treatment, the particle size of the flame retardant cannot be sufficiently reduced, and there is room for improvement in stably discharging the photosensitive resin composition having flame retardancy by the inkjet method.
In recent years, electronic components connected to printed wiring boards have been diversified due to the high performance of electronic devices. Therefore, the printed wiring board is required to have versatility to be able to mount a variety of electronic components. In order to provide versatility to the printed wiring board, the surface of an insulating coating film formed on the printed wiring board may be subjected to surface treatment such as gold plating. Therefore, the cured coating film of the photosensitive resin composition is required to have not only flame retardancy but also gold plating resistance in some cases.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2006/075654
Disclosure of Invention
Problems to be solved by the invention
In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition capable of forming a cured product which is excellent in coating properties for ink jet, flame retardancy, and gold plating resistance without impairing basic properties such as adhesion to a substrate having a circuit pattern and electrical insulation properties.
Means for solving the problems
The gist of the configuration of the present invention is as follows.
[1] A photosensitive resin composition for inkjet, which contains (A) a (meth) acrylic compound having a weight average molecular weight of 500 or more, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, (C) a phosphorus-containing flame retardant, (D) an amine-modified (meth) acrylic compound, and (E) a photopolymerization initiator, wherein the (C) phosphorus-containing flame retardant has a functional group that is curable with active energy rays, and the (D) amine-modified (meth) acrylic compound has a functional group that is curable with active energy rays.
[2] The photosensitive resin composition for inkjet according to [1], wherein the phosphorus-containing flame retardant (C) is in a powder form and has a solubility of 10 parts by mass or more in terms of dissolving 100 parts by mass of the (meth) acrylic compound (B) having a weight average molecular weight of less than 500 at 25 ℃.
[3] The photosensitive resin composition for inkjet according to [1] or [2], wherein the (D) amine-modified (meth) acrylic compound is in a liquid state at 25 ℃ under 1 atmosphere.
[4] The photosensitive resin composition for inkjet according to any one of [1] to [3], wherein the (C) phosphorus-containing flame retardant is a compound having an ethylenically unsaturated bond and/or an oxirane ring.
[5] The photosensitive resin composition for inkjet according to any one of [1] to [3], wherein the (C) phosphorus-containing flame retardant is a compound having a (meth) acryloyl group or a glycidyl group.
[6] The photosensitive resin composition for inkjet according to any one of [1] to [5], wherein the (D) amine-modified (meth) acrylic compound is a compound having an ethylenically unsaturated bond and/or an oxirane ring.
[7] The photosensitive resin composition for inkjet according to any one of [1] to [5], wherein the (D) amine-modified (meth) acrylic compound is a compound having a (meth) acryloyl group or a glycidyl group.
[8] The photosensitive resin composition for inkjet according to any one of [1] to [7], wherein the (meth) acrylic compound (B) having a weight average molecular weight of less than 500 has a cyclic skeleton.
[9] The photosensitive resin composition for inkjet according to any one of [1] to [8], wherein the (E) photopolymerization initiator contains phosphorus.
[10] A cured product of the photosensitive resin composition for inkjet according to any one of [1] to [9 ].
[11] A printed wiring board comprising the cured product of [10 ].
The active energy ray in the above mode [1] represents an ultraviolet ray or a laser having a wavelength of 300 to 400 μm. In the above aspect [2], the powdery (C) phosphorus-containing flame retardant has the following characteristics: since 10 parts by mass or more is dissolved at 25 ℃ relative to 100 parts by mass of the (meth) acrylic compound having a weight average molecular weight of less than 500 (B), the phosphorus-containing flame retardant (C) has a characteristic of being easily dissolved relative to the (meth) acrylic compound having a weight average molecular weight of less than 500 (B) which is a component of the photosensitive resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The photosensitive resin composition of the present invention contains (a) a (meth) acrylic compound having a weight average molecular weight of 500 or more, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, (C) a phosphorus-containing flame retardant having a functional group curable by active energy rays, (D) an amine-modified (meth) acrylic compound having a functional group curable by active energy rays, and (E) a photopolymerization initiator, and thus has excellent applicability to inkjet, and can form a cured product having excellent flame retardancy and gold plating resistance without impairing basic properties such as adhesion to a substrate having a circuit pattern and electrical insulation properties.
According to the photosensitive resin composition of the present invention, the phosphorus-containing flame retardant (C) is in the form of powder and has a solubility of dissolving 10 parts by mass or more per 100 parts by mass of the (meth) acrylic compound (B) having a weight average molecular weight of less than 500 at 25 ℃.
According to the photosensitive resin composition of the present invention, (D) the amine-modified (meth) acrylic compound is in a liquid state at 25 ℃ under 1 atm, and thus, the coating property by the inkjet method is more excellent, and a cured product with reliably improved flame retardancy can be formed.
According to the photosensitive resin composition of the present invention, the phosphorus-containing flame retardant (C) is a compound having an ethylenically unsaturated bond and/or an oxirane ring, so that the coating property by an ink jet method can be reliably improved, and the gold plating resistance can be reliably improved by curing more reliably with an active energy ray.
According to the photosensitive resin composition of the present invention, the (D) amine-modified (meth) acrylic compound is a compound having an ethylenically unsaturated bond and/or an oxirane ring, and thus the coating property by the inkjet method can be reliably improved, and the gold plating resistance can be reliably improved by curing more reliably with an active energy ray.
According to the photosensitive resin composition of the present invention, (B) the (meth) acrylic compound having a weight average molecular weight of less than 500 has a cyclic skeleton, and thus the gold plating resistance can be further improved.
Detailed Description
Next, the photosensitive resin composition of the present invention will be described in detail below. The photosensitive resin composition of the present invention is an inkjet photosensitive resin composition containing (a) a (meth) acrylic compound having a weight average molecular weight of 500 or more, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, (C) a phosphorus-containing flame retardant, (D) an amine-modified (meth) acrylic compound, and (E) a photopolymerization initiator, (C) the phosphorus-containing flame retardant has a functional group curable with active energy rays, and (D) the amine-modified (meth) acrylic compound has a functional group curable with active energy rays. The photosensitive resin composition of the present invention can form a cured product which does not impair basic properties such as adhesion to a substrate having a circuit pattern and electrical insulation properties and which is excellent in coating properties for ink jet, flame retardancy and gold plating resistance.
(A) (meth) acrylic compound having weight average molecular weight of 500 or more
(A) The chemical structure of the (meth) acrylic compound having a weight average molecular weight of 500 or more (hereinafter sometimes referred to as "(meth) acrylic compound (a)") is not particularly limited as long as it is a (meth) acrylic compound having a weight average molecular weight of 500 or more. In the present specification, "weight average molecular weight" means a weight average molecular weight measured by Gel Permeation Chromatography (GPC) at normal temperature and calculated by polystyrene conversion.
Examples of the (meth) acrylic compound (a) include a polymer of a (meth) acrylic acid-containing monomer, a polymer of a (meth) acrylate-containing monomer, a polymer of a (meth) acrylic acid-and (meth) acrylate-containing monomer, an epoxy (meth) acrylate obtained by reacting a (meth) acrylic acid with an epoxy resin, a urethane (meth) acrylate, and the like. Among these, from the viewpoint of reliably improving the coatability by the inkjet method, a (meth) acrylate compound is preferable, and epoxy (meth) acrylate and urethane (meth) acrylate are particularly preferable.
The epoxy (meth) acrylate can be obtained by reacting (meth) acrylic acid with at least a part of epoxy groups of an epoxy resin having 1 or more epoxy groups in one molecule. The epoxy resin is not particularly limited, and examples thereof include biphenyl aralkyl type epoxy resins, phenyl aralkyl type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, silicone-modified epoxy resins, and other rubber-modified epoxy resins, e-caprolactone-modified epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cycloaliphatic polyfunctional epoxy resins, glycidyl ester type polyfunctional epoxy resins, glycidyl amine type polyfunctional epoxy resins, heterocyclic type polyfunctional epoxy resins, bisphenol-modified novolac type epoxy resins, polyfunctional modified novolac type epoxy resins, and the like. The epoxy resins may be used alone or in combination of 2 or more. Thus, the epoxy (meth) acrylate as the (meth) acrylic compound (a) has no free carboxyl group.
Examples of the urethane (meth) acrylate include urethane (meth) acrylates obtained by reacting a compound having 2 or more isocyanate groups in 1 molecule (polyisocyanate compound), a compound having 2 or more hydroxyl groups in 1 molecule (polyol compound), and (meth) acrylic acid.
The polyisocyanate compound is not particularly limited, and examples thereof include Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Methylene Diisocyanate (MDI), methylene dicyclohexyl isocyanate, trimethylhexamethylene diisocyanate, hexane diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl isocyanate, toluene diisocyanate, 1, 2-diphenylethane diisocyanate, 1, 3-diphenylpropane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethyl diisocyanate, and the like. The polyisocyanate compounds may be used alone or in combination of 2 or more.
The polyhydric alcohol compound is not particularly limited, and examples thereof include alkanediols having 2 to 22 carbon atoms such as ethylene glycol, propylene glycol, trimethylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, neopentyl glycol, 1, 6-hexanediol, 2-diethyl-1, 3-propanediol, 3-dimethylolheptane, 2-ethyl-2-butyl-1, 3-propanediol, 1, 12-dodecanediol, 1, 18-octadecanediol, 2-butene-1, 4-diol, 2, 6-dimethyl-1-octene-3, aliphatic diols such as olefin diols such as 8-diol; alicyclic diols such as 1, 4-cyclohexanediol and 1, 4-cyclohexanedimethanol; aliphatic triols such as glycerol, 2-methyl-2-hydroxymethyl-1, 3-propanediol, 2, 4-dihydroxy-3-hydroxymethylpentane, 1,2, 6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1, 3-propanediol, 2, 4-dihydroxy-3- (hydroxymethyl) pentane and 2, 2-bis (hydroxymethyl) -3-butanol; polyols having 4 or more hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol, and xylitol. The polyol compounds may be used alone or in combination of 2 or more. Thus, the urethane (meth) acrylate as the (meth) acrylic compound (a) has no free carboxyl group.
Further, as the urethane (meth) acrylate, for example, urethane (meth) acrylates having the following structure can be cited: the epoxy resin composition has a structure obtained by reacting (meth) acrylic acid with at least a part of epoxy groups of an epoxy resin having 1 or more epoxy groups in 1 molecule to obtain an epoxy (meth) acrylate, and subjecting a compound having 1 or more isocyanate groups in 1 molecule to an addition reaction with the generated hydroxyl groups.
The epoxy resin is not particularly limited, and examples thereof include, as with the above epoxy (meth) acrylate, rubber-modified epoxy resins such as biphenyl aralkyl type epoxy resins, phenyl aralkyl type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, silicone-modified epoxy resins, and the like, epsilon-caprolactone-modified epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, cyclic aliphatic polyfunctional epoxy resins, glycidyl ester type polyfunctional epoxy resins, glycidyl amine type polyfunctional epoxy resins, heterocyclic type polyfunctional epoxy resins, bisphenol modified novolac type epoxy resins, polyfunctional modified novolac type epoxy resins, and the like. The epoxy resins may be used alone or in combination of 2 or more.
The compound having 1 or more isocyanate groups in 1 molecule is not particularly limited, and examples thereof include Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Methylene Diisocyanate (MDI), methylene dicyclohexyl isocyanate, trimethyl hexamethylene diisocyanate, hexane diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl isocyanate, toluene diisocyanate, 1, 2-diphenylethane diisocyanate, 1, 3-diphenylpropane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethyl diisocyanate, and the like, as described above. The isocyanate compounds may be used alone or in combination of 2 or more. Thus, the urethane (meth) acrylate having a structure obtained by addition reaction of a compound having 1 or more isocyanate groups in 1 molecule and a hydroxyl group of epoxy (meth) acrylate as the (meth) acrylic compound (a) does not have a free carboxyl group.
The various (meth) acrylic compounds (A) may be used alone or in combination of 2 or more.
The weight average molecular weight of the (meth) acrylic compound (a) is not particularly limited as long as it is 500 or more, but is preferably 520 or more, more preferably 700 or more, and particularly preferably 1000 or more, from the viewpoint of further improving the ejection property by the ink jet method. On the other hand, from the viewpoint of reliably preventing an increase in viscosity of the photosensitive resin composition and obtaining excellent coatability even in the inkjet method, the upper limit of the weight average molecular weight of the (meth) acrylic compound (a) is preferably 5000, and particularly preferably 4000. The number of functional groups of the (meth) acrylic compound (a) is not particularly limited, but is preferably 1 to 5, and more preferably 2 to 4, from the viewpoint of further improving solder heat resistance and gold plating resistance.
(B) (meth) acrylic compound having weight average molecular weight of less than 500
(B) The chemical structure of the (meth) acrylic compound having a weight average molecular weight (Mw) of less than 500 (hereinafter sometimes referred to as "(meth) acrylic compound (B)") is not particularly limited as long as it is a (meth) acrylic compound having a weight average molecular weight of less than 500. Examples of the (meth) acrylic compound (B) include (meth) acrylate compounds such as monofunctional (meth) acrylate monomers and 2 or more functional (meth) acrylate monomers. By blending the (meth) acrylic compound (B) in the photosensitive resin composition of the present invention, a predetermined amount of the predetermined phosphorus-containing flame retardant (C) described later can be dissolved in the (meth) acrylic compound (B), and therefore, a photosensitive resin composition excellent in coating properties in an ink jet method can be obtained, and flame retardancy can be imparted to the photosensitive resin composition. Further, since the viscosity of the photosensitive resin composition at 25 ℃ is lowered by blending the (meth) acrylic compound (B), the photosensitive resin composition can be used for ink jet without blending a non-reactive diluent (for example, an organic solvent).
The viscosity of the (meth) acrylic compound (B) at 25 ℃ is not particularly limited, but is preferably 1.0mPa · s or more and 50mPa · s or less, and particularly preferably 2.0mPa · s or more and 30mPa · s or less, from the viewpoint of further improving the coating property in the ink jet method and obtaining excellent bleeding resistance.
Examples of the (meth) acrylic compound (B) include monofunctional (meth) acrylate compounds such as benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenol (meth) acrylate, phenoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, and mixtures thereof, 2-functional (meth) acrylate compounds such as allylated cyclohexyl di (meth) acrylate and isocyanurate di (meth) acrylate, and 3-or more-functional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate. The above-mentioned substances may be used alone or in combination of 2 or more. Among them, from the viewpoint of further improving the gold plating resistance, the (meth) acrylic compound (B) having a cyclic skeleton is preferable, and the (meth) acrylic compound (B) having an aromatic ring is particularly preferable.
The content of the (meth) acrylic compound (a) and the (meth) acrylic compound (B) in the photosensitive resin composition is not particularly limited, and from the viewpoint of reliably imparting strength to a cured product of the photosensitive resin composition, the (meth) acrylic compound (a) is preferably contained by 5.0 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more, relative to 100 parts by mass of the (meth) acrylic compound (B). On the other hand, from the viewpoint of reliably imparting flame retardancy by dissolving a predetermined phosphorus-containing flame retardant (C) described later in the (meth) acrylic compound (B) and reliably improving coatability in the inkjet method, the content of the (meth) acrylic compound (a) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the (meth) acrylic compound (B).
(C) Phosphorus-containing flame retardants
In the present invention, as the phosphorus-containing flame retardant of component (C), a phosphorus-containing flame retardant having a functional group curable by an active energy ray (hereinafter, sometimes referred to as "phosphorus-containing flame retardant (C)") is used. By blending the phosphorus-containing flame retardant (C) in the photosensitive resin composition, excellent coatability can be obtained even in the inkjet method, and the composition contributes to the provision of gold plating resistance and flame retardancy. The phosphorus-containing flame retardant (C) may be a compound containing an ethylenically unsaturated bond and/or an oxirane ring (epoxy group) from the viewpoint of reliably improving the coatability by an ink-jet method and further reliably improving the gold plating resistance by curing with an active energy ray. More specifically, the phosphorus-containing flame retardant (C) containing an ethylenically unsaturated bond and/or an oxirane ring may be a compound having a (meth) acryloyl group, a chain epoxy group, or an alicyclic epoxy group.
From the viewpoint of reliably obtaining excellent coatability in the ink jet method and reliably imparting flame retardancy to the photosensitive resin composition, it is preferable that the phosphorus-containing flame retardant (C) is in the form of powder and has a solubility of 10 parts by mass or more dissolved in 100 parts by mass of the (meth) acrylic compound (B) at 25 ℃. The phosphorus-containing flame retardant (C) is in the form of powder before being mixed into the photosensitive resin composition of the present invention. However, even after the phosphorus-containing flame retardant (C) is blended into the photosensitive resin composition of the present invention, since a part of the phosphorus-containing flame retardant (C) remains in a powder state and exists in the photosensitive resin composition of the present invention (that is, another part of the phosphorus-containing flame retardant (C) exists in the photosensitive resin composition of the present invention in a dissolved state), it can be confirmed that the phosphorus-containing flame retardant (C) is in a powder state before being mixed into the photosensitive resin composition of the present invention even after the phosphorus-containing flame retardant (C) is blended into the photosensitive resin composition of the present invention.
From the viewpoint of further improving the coatability by the ink-jet method, the solubility of the phosphorus-containing flame retardant (C) is preferably 12 parts by mass or more, and particularly preferably 14 parts by mass or more, with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ℃. On the other hand, the higher the upper limit value of the solubility of the phosphorus-containing flame retardant (C) with respect to 100 parts by mass of the (meth) acrylic compound (B) at 25 ℃ is, the more preferable is, for example, 50 parts by mass. Therefore, in the photosensitive resin composition, a part of the phosphorus-containing flame retardant (C) is dissolved, and the other part is mixed in a state of powder.
The average particle diameter of the powdery phosphorus-containing flame retardant (C) is not particularly limited, but is preferably 0.10 μm or more and 3.00 μm or less, and particularly preferably 0.10 μm or more and 1.00 μm or less, from the viewpoint of dispersibility in the photosensitive resin composition, for example.
Specific examples of the phosphorus-containing flame retardant (C) in the form of powder in which 10 parts by mass or more of the phosphorus-containing flame retardant (C) is dissolved in 100 parts by mass of the (meth) acrylic compound (B) at 25 ℃ include (meth) acryloylmethyldiphenylphosphine oxide, 2- (3, 4-epoxycyclohexyl) ethyldiphenylphosphine oxide, 10- (3-glycidoxypropyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- [2- (3, 4-epoxycyclohexyl) ethyl ] -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3-glycidoxypropyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like, 9, 10-dihydro-9-oxa-10-vinyl-10-phosphaphenanthrene-10-oxide, phenyl vinyl phosphinic acid, and the like. The above-mentioned substances may be used alone or in combination of 2 or more. Among them, (meth) acryloyl methyldiphenylphosphine oxide and 10- (3-glycidoxypropyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are preferable from the viewpoint that the coating properties in the ink jet method are more excellent and a cured product having more excellent gold plating resistance can be obtained.
The content of the phosphorus-containing flame retardant (C) is not particularly limited, and the lower limit value of the phosphorus-containing flame retardant (C) is preferably 5.0 parts by mass, more preferably 10 parts by mass, and particularly preferably 15 parts by mass, relative to 100 parts by mass of the (meth) acrylic compound (B), from the viewpoint of reliably contributing to improvement of flame retardancy. On the other hand, from the viewpoint of further improving the coating properties by the ink jet method, the upper limit of the content of the phosphorus-containing flame retardant (C) is preferably 40 parts by mass, more preferably 35 parts by mass, and particularly preferably 30 parts by mass, relative to 100 parts by mass of the (meth) acrylic compound (B).
(D) Amine-modified (meth) acrylic compound
In the present invention, as the amine-modified (meth) acrylic compound as the component (D), an amine-modified (meth) acrylic compound having a functional group that is cured by an active energy ray (hereinafter, sometimes referred to as "amine-modified (meth) acrylic compound (D)") is used. By blending the amine-modified (meth) acrylic compound (D) in the photosensitive resin composition, excellent coatability can be obtained even in the inkjet method, and it contributes to imparting gold plating resistance and flame retardancy. The amine-modified (meth) acrylic compound (D) is different from the (meth) acrylic compound (a) and the (meth) acrylic compound (B) in the aspect of amine modification. Therefore, the (meth) acrylic compound (a) and the (meth) acrylic compound (B) are not modified with an amine.
The amine-modified (meth) acrylic compound (D) is preferably a compound having an ethylenically unsaturated bond and/or an oxirane ring, from the viewpoint that the coating properties by the ink jet method can be reliably improved, and the gold plating resistance can be reliably improved by curing with an active energy ray. More specifically, the amine-modified (meth) acrylic compound (D) having an ethylenically unsaturated bond and/or an oxirane ring includes a compound having a (meth) acryloyl group or glycidyl group.
As the amine-modified (meth) acrylic compound (D), an amine-modified (meth) acrylic compound (D) which is liquid at 25 ℃ under 1 atm is preferable from the viewpoint of reliably obtaining excellent coatability in the inkjet method and reliably imparting flame retardancy to the photosensitive resin composition. Specific examples of the amine-modified (meth) acrylic compound (D) include CN371, CN550, CN551 (manufactured by Sartomer Company, supra), EBECRYL3703, EBECRYL80, EBECRYL7100 (manufactured by Daicel-Allnex Ltd., supra), SP281, SP283, and SE1703 (manufactured by SOLTECH corporation, supra).
The content of the amine-modified (meth) acrylic compound (D) is not particularly limited, and from the viewpoint of reliably contributing to improvement of flame retardancy, the lower limit value of the amine-modified (meth) acrylic compound (D) is preferably 1.0 part by mass, more preferably 3.0 parts by mass, and particularly preferably 5.0 parts by mass, relative to 100 parts by mass of the (meth) acrylic compound (B). On the other hand, from the viewpoint of further improving the coatability by the ink-jet method, the upper limit of the content of the amine-modified (meth) acrylic compound (D) is preferably 25 parts by mass, more preferably 20 parts by mass, and particularly preferably 15 parts by mass, relative to 100 parts by mass of the (meth) acrylic compound (B).
(E) Photopolymerization initiator
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be suitably used. Examples of the photopolymerization initiator include bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 2-methyl-4' - (methylthio) -2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4' -bis (diethylamino) benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, ethyl p-dimethylaminobenzoate, and the like. The above-mentioned substances may be used alone or in combination of 2 or more. Among the above photopolymerization initiators, those having phosphorus are preferable from the viewpoint of flame retardancy.
The content of the photopolymerization initiator is not particularly limited, and is preferably 5.0 parts by mass or more and 30 parts by mass or less, and particularly preferably 10 parts by mass or more and 20 parts by mass or less, with respect to 100 parts by mass of the (meth) acrylic compound (B).
In the photosensitive resin composition for inkjet of the present invention, other components such as a colorant, various additives, a non-reactive diluent, and the like may be blended as necessary in addition to the components (a) to (E).
The colorant is not particularly limited to pigments, and the like. The colorant may be any color such as a white colorant, a blue colorant, a green colorant, a yellow colorant, a violet colorant, or a black colorant, depending on the color to be imparted to the cured product of the photosensitive resin composition. Examples of the colorant include titanium oxide as a white colorant, inorganic colorants such as carbon black as a black colorant, phthalocyanine green as a green colorant, phthalocyanines such as phthalocyanine blue and raonol blue as a blue colorant, phthalocyanines such as phthalocyanine yellow as a yellow colorant, and organic colorants such as anthraquinones.
Examples of the various additives include defoaming agents such as silicone, hydrocarbon and acrylic, inorganic fillers such as talc, barium sulfate, alumina, aluminum hydroxide, mica and silica, powdery urethane resins, (meth) acrylic polymers, vinyl polymers, modified carboxyl group-containing polymers, and organic fillers such as carboxylic acid esters.
If necessary, a non-reactive diluent is added to adjust the viscosity and drying property of the photosensitive resin composition for inkjet. Examples of the non-reactive diluent include an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropyl alcohol and cyclohexanol, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, cellosolve such as butyl cellosolve, carbitols such as carbitol and butyl carbitol, and esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate.
The method for producing the photosensitive resin composition for inkjet according to the present invention is not limited to a specific method, and for example, the photosensitive resin composition for inkjet can be produced by mixing the above components at a predetermined ratio and then kneading or mixing them at room temperature by a kneading means such as a triple roll, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer or a planetary mixer. Further, pre-kneading or pre-mixing may be performed as necessary before the kneading or mixing.
Next, the method of using the photosensitive resin composition for ink jet of the present invention will be describedAnd (5) clearing. For example, an insulating coating (e.g., a solder resist) can be formed on a substrate (e.g., a printed wiring board having a predetermined conductor circuit pattern) by an ink jet printing method using the photosensitive resin composition for ink jet of the present invention. First, the photosensitive resin composition for inkjet of the present invention is applied to a printed wiring board in a desired pattern by an inkjet method (for example, an inkjet method using a jet dispenser). After coating, the coated film is photocured by Laser Direct writing using LDI (Laser Direct Imaging) or by active energy rays such as ultraviolet rays having a wavelength of 300 to 400 μm. In the case of performing the photo-curing treatment by using an active energy ray such as ultraviolet ray, the irradiation light amount is, for example, 100 to 2000mJ/cm2The range of (1). After the photocuring treatment of the coating film, post-curing (thermosetting treatment) is performed at 130 to 170 ℃ for 20 to 80 minutes by a hot air circulation dryer or the like, whereby a solder resist having a desired pattern can be formed on the printed wiring board.
Examples
Next, examples of the present invention will be described, and the present invention is not limited to the above examples as long as the invention does not depart from the gist thereof.
Examples 1 to 26 and comparative examples 1 to 6
The photosensitive resin compositions used in examples 1 to 26 and comparative examples 1 to 6 were prepared by mixing the components shown in tables 1 to 3 at the mixing ratios shown in tables 1 to 3 and mixing and dispersing them at room temperature by a bead mill. Unless otherwise specified, the blending amounts of the respective components shown in tables 1 to 3 below represent parts by mass. In addition, the following table 1 ~ 3 in the amount of mixing in the empty column part shows not mixing.
Further, the details of each component in tables 1 to 3 are as follows.
(A) (meth) acrylic compound having weight average molecular weight of 500 or more
·EBECRYL 3708、EBECRYL 8405、EBECRYL 8402：Daicel-Allnex Ltd.
Miramer PE210, Miramer PE250, Miramer PU 210: miwon corporation
(B) (meth) acrylic compound having weight average molecular weight of less than 500
Viscoat #160, Viscoat #150, IBXA: osaka organic chemical co
Light Ester 1.4BG, Light Ester 2 EG: kyoeisha chemical Co Ltd
Aronix M-220: toyo Synthesis Co Ltd
·HDDA：Daicel-Allnex Ltd.
Miramer M140: miwon corporation
(C) Phosphorus-containing flame retardants
MC-4: the solubility of the (meth) acrylic compound having a weight-average molecular weight of less than 500 to 100g of (B) at 25 ℃ is 10 to 15g, and the solubility is measured by Tanshan chemical industries, Ltd
E-10 g: the solubility of the (meth) acrylic compound having a weight-average molecular weight of less than 500 to 100g of (B) at 25 ℃ is 10 to 15g, and the solubility is measured by Tanshan chemical industries, Ltd
(D) Amine-modified (meth) acrylic compound
EBECRYL 3703: amine-modified bisphenol A type epoxy acrylate was liquid at 25 ℃ under 1 atmosphere, and Daicel-Allnex Ltd.
CN 371: amine-modified di (meth) acrylate (amine value 136mgKOH/g), liquid at 25 ℃ under 1 atmosphere, Sartomer Company
(E) Photopolymerization initiator
IRGACURE907, IRGACURE369E, LUCIRIN TPO, IRGACURE 819: basff Corp Ltd
Chemcure DETX: chembridge International Inc
Coloring agent
Raonol blue FG-7351: TOYO COLOR co Ltd
Aesthetic yellow penetration (cromophthal yellow) AGR: ciba specialty Chemicals Co., Ltd
Additive agent
FLOWLEN G-700: kyoeisha chemical Co Ltd
UVX-189: nanben chemical plant Kabushiki Kaisha
BYK-361N, BYK-168: nikk chemical Japan K.K.
Non-reactive diluents
EDGAC: shengang organic chemical industry society
Phosphorus-containing flame retardant having no functional group curable with active energy rays
OP-935: aluminum diethylphosphinate, Craine
FP-110: hexaphenoxy cyclotriphosphazene, Sanguano
Amine-modified (meth) acrylic compound having no functional group curable with active energy ray
PA-100: polymerized fatty acid polyamide resin, T & K TOKA Kabushiki Kaisha
Flamestab NOR 116 FF: hindered amine flame retardants, Basff Corp
Sample preparation Process
Substrate: copper clad laminate (thickness 1.6mm)
Surface treatment: abrasive scrub
A printing method: ink-jet printing (ink-jet device: "MJP 2013F 1-DU", Microcraft company)
Dry film thickness: 20 to 23 μm
Exposure: on the coating film at 1000mJ/cm2"UB 093-5 AM" manufactured by EYE GRAPHICS K.K.) "
Post-curing: BOX-TYPE DRYING FURNACE FOR 60 min at 150 deg.C
Evaluation item
(1) Coating property
A 100 × 100 dot pattern was applied by the ink jet device, and the substrate thereafter was observed with a magnifying glass (30 times) to confirm whether or not the pattern equivalent application was performed.
(2) Adhesion Property
The adhesion to copper of the samples prepared in the above-described sample preparation step was evaluated in accordance with JIS K5400, and the remaining number of the checkerboard was evaluated in the following manner.
◎：100/100
○：70/100～99/100
△：10/100～69/100
×：0/100～9/100
(3) Flame retardancy
In addition to changing the substrate from a copper-clad laminate to a polyimide substrate having a thickness of 25 μm, coating was performed on both sides so that the dry film thickness became 20 μm in accordance with the above-described sample preparation process, and after forming a cured coating film, evaluation was performed in accordance with the UL94VTM test standard.
(4) Electrical insulation
In addition to changing the substrate from the copper-clad laminate to a comb-shaped test pattern (line width of 100 μm and line pitch of 100 μm), a cured coating was formed in the above-described sample preparation step, and after applying a direct current of 30V in an atmosphere at a temperature of 85 ℃ and a humidity of 85% and leaving for 100 hours, the sample was taken out of the cell and the insulation resistance value was measured.
(5) Resistance to gold plating
The sample prepared in the above sample preparation step was subjected to gold plating such that the thickness of the nickel layer was 3 to 5 μm and the thickness of the gold plating layer was 0.05 μm, and the substrate thereafter was observed with a magnifying glass (30 times) to confirm whether or not the gold plating was deposited on the copper pad opened.
Very good: formation of gold plating layer
O: slightly without forming gold plating layer
And (delta): a part of which is not formed with gold plating
X: the whole surface is not provided with gold plating
The evaluation results are shown in tables 1,2 and 3 below.
[ Table 1]
[ Table 2]
[ Table 3]
From tables 1 and 2 above, in examples 1 to 26, which are photosensitive resin compositions containing (a) a (meth) acrylic compound having a weight average molecular weight of 500 or more, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, (C) a phosphorus-containing flame retardant having a functional group curable with an active energy ray, (D) an amine-modified (meth) acrylic compound having a functional group curable with an active energy ray, and (E) a photopolymerization initiator, the cured products having excellent coating properties for inkjet, no deterioration in adhesion and electrical insulation properties, and excellent flame retardancy and gold plating resistance can be formed. According to example 3 and examples 1,2, 4 to 6, the gold plating resistance was further improved when MC-4, which is methacryloyl methyldiphenylphosphine oxide, was contained as the phosphorus-containing flame retardant of the component (C) and CN371, which is an amine-modified acrylate, was contained as the amine-modified (meth) acrylic compound of the component (D). In particular, according to examples 1 and 13 to 19, when benzyl acrylate having a structure with a cyclic skeleton is used as (B) the (meth) acrylic compound having a weight average molecular weight of less than 500, the gold plating resistance is further improved.
On the other hand, according to the above table 3, flame retardancy could not be obtained in comparative example 1 containing no amine-modified (meth) acrylic compound as the component (D) and comparative example 2 containing no phosphorus-containing flame retardant as the component (C). In comparative examples 3 and 4 in which an amine-modified (meth) acrylic compound having no functional group curable with an active energy ray was added in place of the amine-modified (meth) acrylic compound of component (D), gold plating resistance and coating properties in an inkjet method could not be obtained. In comparative examples 5 and 6 in which a phosphorus-containing flame retardant having no functional group curable with an active energy ray was added in place of the phosphorus-containing flame retardant of component (C), gold plating resistance and coating properties in an inkjet method could not be obtained.
Industrial applicability
The photosensitive resin composition of the present invention has excellent applicability by an ink jet method, and can form a cured product having excellent flame retardancy and gold plating resistance without impairing adhesion to a circuit pattern and electrical insulation properties, and therefore, has high utility value in the field of forming an insulating coating on, for example, a printed wiring board having a desired circuit pattern.
Claims (11)
1. A photosensitive resin composition for inkjet, which contains (A) a (meth) acrylic compound having a weight average molecular weight of 500 or more, (B) a (meth) acrylic compound having a weight average molecular weight of less than 500, (C) a phosphorus-containing flame retardant, (D) an amine-modified (meth) acrylic compound, and (E) a photopolymerization initiator, wherein the (C) phosphorus-containing flame retardant has a functional group that is cured by active energy rays, and the (D) amine-modified (meth) acrylic compound has a functional group that is cured by active energy rays.
2. The photosensitive resin composition for inkjet according to claim 1, wherein the phosphorus-containing flame retardant (C) is in the form of a powder and has a solubility of 10 parts by mass or more per 100 parts by mass of the (meth) acrylic compound (B) having a weight average molecular weight of less than 500 at 25 ℃.
3. The photosensitive resin composition for inkjet according to claim 1 or 2, wherein the (D) amine-modified (meth) acrylic compound is in a liquid state at 25 ℃ under 1 atmosphere.
4. The photosensitive resin composition for inkjet according to any one of claims 1 to 3, wherein the (C) phosphorus-containing flame retardant is a compound having an ethylenically unsaturated bond and/or an oxirane ring.
5. The photosensitive resin composition for inkjet according to any one of claims 1 to 3, wherein the (C) phosphorus-containing flame retardant is a compound having a (meth) acryloyl group or a glycidyl group.
6. The photosensitive resin composition for inkjet according to any one of claims 1 to 5, wherein the (D) amine-modified (meth) acrylic compound is a compound having an ethylenically unsaturated bond and/or an oxirane ring.
7. The photosensitive resin composition for inkjet according to any one of claims 1 to 5, wherein the (D) amine-modified (meth) acrylic compound is a compound having a (meth) acryloyl group or a glycidyl group.
8. The photosensitive resin composition for inkjet according to any one of claims 1 to 7, wherein the (meth) acrylic compound (B) having a weight average molecular weight of less than 500 has a cyclic skeleton.
9. The photosensitive resin composition for inkjet according to any one of claims 1 to 8, wherein the (E) photopolymerization initiator contains phosphorus.
10. A cured product of the photosensitive resin composition for inkjet according to any one of claims 1 to 9.
11. A printed wiring board comprising the cured product according to claim 10.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2020-159065 | 2020-09-23 | ||
| JP2020159065A JP7220691B2 (en) | 2020-09-23 | 2020-09-23 | Photosensitive resin composition |
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| JP5620700B2 (en) * | 2010-03-30 | 2014-11-05 | 富士フイルム株式会社 | Ink composition for ink jet recording, ink jet recording method, and printed matter |
| JP2012140491A (en) * | 2010-12-28 | 2012-07-26 | Fujifilm Corp | Ink composition, inkjet recording method, and printed material |
| JP2014141568A (en) * | 2013-01-23 | 2014-08-07 | Jnc Corp | Photocurable inkjet ink and use thereof |
| JP6993154B2 (en) * | 2017-09-27 | 2022-01-13 | 株式会社タムラ製作所 | Photosensitive resin composition |
| EP3778805A4 (en) * | 2018-03-30 | 2022-01-19 | Taiyo Ink Mfg. Co., Ltd. | Curable composition for inkjet, cured product of same, and electronic component comprising said cured product |
| JP6918163B2 (en) * | 2019-03-08 | 2021-08-11 | 株式会社タムラ製作所 | Photosensitive resin composition |
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