CN102227681A - Curable resin composition and reflective sheet - Google Patents

Curable resin composition and reflective sheet Download PDF

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Publication number
CN102227681A
CN102227681A CN200980147621XA CN200980147621A CN102227681A CN 102227681 A CN102227681 A CN 102227681A CN 200980147621X A CN200980147621X A CN 200980147621XA CN 200980147621 A CN200980147621 A CN 200980147621A CN 102227681 A CN102227681 A CN 102227681A
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CN
China
Prior art keywords
resin composition
hardening resin
titanium dioxide
base material
solidfied material
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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CN200980147621XA
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Chinese (zh)
Inventor
能坂麻美
角谷武德
宇敷滋
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Priority to CN201310690096.4A priority Critical patent/CN103645605B/en
Publication of CN102227681A publication Critical patent/CN102227681A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A curable resin composition is provided which attains excellent resolution even when titanium oxide is contained therein in a large amount, and which gives a high-resolution cured object having a high reflectance. Also provided is a reflective sheet obtained from the composition. The curable resin composition is characterized by comprising a resin containing an ethylenically unsaturated group and a carboxy group in the molecule, a bisacylphosphine oxide photopolymerization initiator, a monoacylphosphine oxide photopolymerization initiator, titanium oxide, and an organic solvent.

Description

Hardening resin composition and reflector plate
Technical field
The present invention relates to hardening resin composition and reflector plate.
Specifically, be following 4 kinds.
Even the first also can form the hardening resin composition of the meticulous pattern of height and the reflector plate that uses this resin combination for high reflectance.
Even another kind is also can form high meticulous pattern and can obtain the hardening resin composition of the difficult cementability thermoplastic matrix also solidfied material of adaptation excellence and the reflector plate that this resin combination is used for difficult cementability thermoplastic matrix for high reflectance.
Even and another kind is also can form high meticulous pattern and can obtain the hardening resin composition of solidfied material of excellent heat resistance and the reflector plate that uses this resin combination for high reflectance.
Even further another kind is also can form high meticulous pattern and can obtain to be used to have the hardening resin composition of solidfied material of excellent heat resistance of flexible base material and the reflector plate that this resin combination is used to have flexible base material for high reflectance.
Background technology
Using resin combination to form method of patterning on substrate has a variety ofly, can list for example silk screen print method, photoetching process etc.In these methods, photoetching process is compared with other pattern formation methods, has the excellent impact of performance in the following areas, thereby is widely used in the formation etc. of printed-wiring board (PWB), semi-conductive pattern or liquid crystal color filter (with reference to patent documentation 1,2).That is, compare with other pattern formation methods and can obtain high meticulous pattern; Can not need to use galley to determine pattern position and come the aligned pattern position by mask pattern, thereby printing position precision height; The pattern that also can yield rate obtains even precision during pattern forms even without masterful technique well; And do not occur in oozing out of being easy to generate in the serigraphy, thinning.
In this photoetching process, resin combination irradiation UV light waited carry out patterning.And in order to make UV light etc. see through resin combination, resin combination is being carried out use a small amount of as far as possible pigment, dyestuff usually when painted.
Therefore, the purpose of the light that waits for reflection light emitting diode (LED) and containing in the resin combination of a large amount of Chinese whites (titanium dioxide etc.) for example because titanium dioxide absorbs or reflection UV light etc., thereby uses the formation of photolithographic pattern to become difficult.For this reason, also can use photoetching process to form the resin combination of pattern even seek a kind of Chinese white such as a large amount of titanium dioxide that contains.
In addition, the resin combination that contains a large amount of above-mentioned titanium dioxide etc. be used for the light source of backlight liquid crystal display such as portable terminal, computer, televisor, ligthing paraphernalia etc. sometimes, especially for the reflection of light material that effectively utilizes with the luminous LED of low electric power etc.And as one of this reflecting material, the reflector plate that has the solidfied material by this resin combination to form.
And, as the base material that is used for this reflector plate, the base material that forms by thermoplastic resin of polyester base materials such as polyamide-based base material such as polyolefin base material, nylon, polyethylene terephthalate such as tygon etc. (below, be called " thermoplastic matrix ".) in processability, permanance, gazed in price.
Yet, the equal chemical stabilization of these thermoplastic matrixes, thereby be insoluble to organic solvent class, monomer class.And then these base materials have the functional group that can react with the resin combination that is used for reflector plate hardly, thus this resin combination with and the driving fit of solidfied material and this base material be difficult.In addition, in this instructions, the thermoplastic matrix that such resin combination is difficult to driving fit is called " difficult cementability thermoplastic matrix ", and can list polyolefin base material, polyamide-based base material, polyester is base material etc.
In addition, difficult cementability thermoplastic matrix has thermoplasticity, even thereby this base material do not reach fusing point, the distortion that is easy to generate the contraction that causes by thermal conductance yet, causes by stretching.Therefore, by heat curing difficult cementability thermoplastic matrix is carried out high meticulous pattern and form the difficulty that becomes.For this reason, also can use photoetching process to form high meticulous pattern and the resin combination that difficult cementability thermoplastic matrix is had high adaptation even seek a kind of Chinese white such as a large amount of titanium dioxide that contains.
In addition, for bonding agent bonding between the polyester base material that makes as difficult cementability thermoplastic matrix, proposed for example to relate to the scheme (with reference to patent documentation 3) of the particular adhesive of using vibrin.
Further as mentioned above, the resin combination that contains a large amount of titanium dioxide etc. is sometimes being used for utilizing the reflection of light material of LED etc. to use, as one of this reflecting material, and the reflector plate that has the solidfied material by this resin combination to form.And, as the base material that is used for this reflector plate, follow the miniaturization of electronic equipments such as portable terminal, have flexible base material and gazed at.
Here, the solidfied material of such resin combination requires thermotolerance according to the purposes of the base material that forms pattern etc. sometimes.And in this case,, in this resin combination, cooperate epoxy compound sometimes for giving stable on heating purpose to this solidfied material.
Use contain the resin combination of this epoxy compound and the solidfied material that obtains in aspect excellences such as thermotolerance, chemical proofings.Yet there are the following problems: because this solidfied material is crisp thereby can not be used in and have flexible base material.For this reason, also can use photoetching process to form high meticulous pattern, excellent heat resistance and can be used in resin combination even seek a kind of Chinese white such as a large amount of titanium dioxide that contains with flexible base material.
More particularly, though seek a kind of contain epoxy compound also can be used in the Kapton that uses roller to process, Copper Foil, aluminium foil etc. to roller technology (roll-to-roll process) have flexible base material, hardening resin composition.
The prior art document
Patent documentation
Patent documentation 1: Japan special fair 1-54390 number
Patent documentation 2: Japan special fair 7-17737 number
Patent documentation 3: TOHKEMY 2007-321004 number
Summary of the invention
The problem that invention will solve
One of purpose of the present invention is, the reflector plate that hardening resin composition is provided and uses this resin combination also can form excellent in resolution and then high reflectance and high meticulous solidfied material even described hardening resin composition contains a large amount of titanium dioxide.
Another object of the present invention is to, the reflector plate that hardening resin composition is provided and this resin combination is used for difficult cementability thermoplastic matrix, even described hardening resin composition contains a large amount of titanium dioxide, also can obtain excellent in resolution and high reflectance and high meticulous so that with the solidfied material of the adaptation excellence of difficult cementability thermoplastic matrix.
In addition, another object of the present invention is to, the reflector plate that hardening resin composition is provided and uses this resin combination even described hardening resin composition contains a large amount of titanium dioxide, also can obtain the solidfied material of excellent in resolution and excellent heat resistance.
And then, another object of the present invention is to, the reflector plate that hardening resin composition is provided and this resin combination is used to have flexible base material, even described hardening resin composition contains a large amount of titanium dioxide, also can obtain excellent in resolution and high reflectance, high meticulous and excellent heat resistance and then can be used in solidfied material with flexible base material.
The scheme that is used to deal with problems
In order to achieve the above object, being used in combination two acylphosphine oxides as Photoepolymerizationinitiater initiater among the present invention is that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater.Thus, even, also can form the pattern of excellent in resolution for containing the hardening resin composition of a large amount of titanium dioxide.
In addition, among the present invention, in above-mentioned hardening resin composition, cooperate urethane acrylate.Thus, even contain a large amount of titanium dioxide, also can form excellent in resolution so that with the adaptation excellent pattern of difficult cementability thermoplastic matrix.
And then, among the present invention, have under the stable on heating situation at the solidfied material that requires hardening resin composition, in above-mentioned hardening resin composition, cooperate epoxy compound.More particularly, in above-mentioned hardening resin composition, cooperate epoxy compound and urethane acrylate.Thus, can form resolution and excellent heat resistance and can be used in pattern with flexible base material.
That is, hardening resin composition of the present invention and reflector plate have following composition.
At first; hardening resin composition of the present invention; it is characterized in that it comprises: resin and two acylphosphine oxide that 1 molecule contains ethylenically unsaturated group and carboxyl are that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater and titanium dioxide and organic solvent.
Specifically, be characterised in that, hardening resin composition of the present invention, with respect to composition 100 mass parts beyond the organic solvent, the use level of titanium dioxide is 40～80 mass parts.
In addition, titanium dioxide is preferably Titanium Dioxide Rutile Top grade.
And then the resin that 1 molecule contains ethylenically unsaturated group and carboxyl is preferably and contains the compound reaction that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and 1 molecule and the copolymerization with carboxyl that obtains is resin.
Further, the compound that has oxirane ring and ethylenically unsaturated group in 1 molecule is preferably the compound that is generated by aliphatics polymerization monomer.
In addition, can cooperate urethane acrylate in the hardening resin composition of the present invention.
Further, requiring its solidfied material to have under the stable on heating situation, can cooperate epoxy compound in the hardening resin composition of the present invention.More particularly, in hardening resin composition of the present invention, can cooperate epoxy compound and antioxidant and urethane acrylate.
Then, reflector plate of the present invention is characterized in that, its solidfied material by above-mentioned hardening resin composition forms.
Specifically, reflector plate of the present invention is characterized in that, it is formed by difficult cementability thermoplastic matrix and the solidfied material that is arranged at the hardening resin composition of the present invention that comprises urethane acrylate of this base material.
Further, reflector plate of the present invention is characterized in that, its solidfied material by the hardening resin composition of the present invention that comprises epoxy compound and antioxidant forms.More particularly, reflector plate of the present invention, it is characterized in that, it is formed by the solidfied material that has flexible base material and be arranged at this base material, and described solidfied material is the solidfied material that comprises the hardening resin composition of the present invention of epoxy compound and antioxidant and urethane acrylate.
In addition; reflector plate of the present invention; it is characterized in that; it is the reflector plate that the solidfied material by hardening resin composition forms, and wherein to comprise resin and two acylphosphine oxide that 1 molecule contains ethylenically unsaturated group and carboxyl be that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater and titanium dioxide to this solidfied material.
More particularly, reflector plate of the present invention is characterized in that, it comprises with respect to the above-mentioned solidfied material of 100 mass parts is the titanium dioxide of 40～80 mass parts.
The invention effect
One of effect of the present invention is, the reflector plate that hardening resin composition can be provided and use this resin combination, even described hardening resin composition contains a large amount of titanium dioxide, also can form excellent in resolution and then high reflectance and high meticulous solidfied material.
Another effect of the present invention is, the reflector plate that hardening resin composition can be provided and this resin combination be used for difficult cementability thermoplastic matrix, even described hardening resin composition contains a large amount of titanium dioxide, also can obtain excellent in resolution and high reflectance and high meticulous so that with the solidfied material of the adaptation excellence of difficult cementability thermoplastic matrix.
In addition, another effect of the present invention is, the reflector plate that hardening resin composition can be provided and use this resin combination, have under the stable on heating situation at the solidfied material that requires hardening resin composition, even described hardening resin composition contains a large amount of titanium dioxide, also can obtain the solidfied material of excellent in resolution and high reflectance, high meticulous and excellent heat resistance.
More particularly, the reflector plate that hardening resin composition can be provided and this resin combination be used to have flexible base material, even described hardening resin composition contains a large amount of titanium dioxide, also can obtain excellent in resolution and high reflectance, high meticulous and excellent heat resistance and then can be used in solidfied material with flexible base material.
Description of drawings
Fig. 1 is the figure that the heating condition of the heating furnace that is used for fast light heat-resistance test among the embodiment (2) is shown.
Embodiment
Below, the present invention is described in detail.
Hardening resin composition of the present invention comprises: resin and two acylphosphine oxide that 1 molecule contains ethylenically unsaturated group and carboxyl are that Photoepolymerizationinitiater initiater and monoacyl phosphine oxide are Photoepolymerizationinitiater initiater and titanium dioxide and organic solvent.In addition, hardening resin composition of the present invention also comprises urethane acrylate comprising on these the basis.In addition, hardening resin composition of the present invention also comprises epoxy compound and antioxidant comprising on the basis of above-mentioned hardening resin composition.More particularly, hardening resin composition of the present invention comprises epoxy compound and antioxidant and urethane acrylate.
In addition, filming of following the application is meant and uses filming that hardening resin composition of the present invention forms.And then solidfied material is meant by photocuring or photocuring and heat curing and makes hardening resin composition of the present invention solidify the solidfied material that forms.
(each composition of composition)
[1 molecule contains the resin of ethylenically unsaturated group and carboxyl]
1 molecule contain ethylenically unsaturated group and carboxyl resin (below, be called " light-cured resin ".) so long as have the ethylenically unsaturated group that is used for photo-curable in 1 molecule and the resin of the carboxyl that is used for developing by weak alkaline aqueous solution gets final product.In addition, as light-cured resin, the preferred resin of enumerating in following (1) to (3) (can be any oligomer or polymkeric substance) that uses is not limited to predetermined substance.
(1) contains the compound reaction that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and 1 molecule and the photosensitive carboxy resin that contains that obtains.
(2) make compound that has 1 epoxy radicals and 1 unsaturated double-bond in 1 molecule and multipolymer with compound of unsaturated double-bond, with the unsaturated monocarboxylic reaction, will react and the photosensitive carboxy resin that contains of acquisition by secondary hydroxyl and the saturated or unsaturated multi-anhydride that this reaction generates.
(3) make the reaction of hydroxyl polymer-containing and saturated or unsaturated multi-anhydride after, the compound that has 1 epoxy radicals and 1 unsaturated double-bond in the carboxylic acid that will be generated by this reaction and 1 molecule reacts and the photosensitive hydroxyl of acquisition and the resin of carboxyl.
In the middle of these, (1) containing in the carboxy resin, is that resin is preferred use as light-cured resin by containing the copolymerization with carboxyl that the compound reaction that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and 1 molecule obtains.
Contain carboxyl (methyl) acrylic acid series copolymer resins for the compound copolymerization that has 1 unsaturated group and 1 above carboxyl in (methyl) acrylate and 1 molecule is obtained.As (methyl) acrylate, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) alkyl-acrylates such as (methyl) Hexyl 2-propenoate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, hydroxyl (methyl) esters of acrylic acids such as caprolactone modification (methyl) acrylic acid 2-hydroxyl ethyl ester, methoxyl diethylene glycol (methyl) acrylate, ethoxy diethylene glycol (methyl) acrylate, different octyloxy diethylene glycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, glycol modification (methyl) esters of acrylic acids such as methoxy poly (ethylene glycol) (methyl) acrylate etc.These can use separately, also can mix multiple use.In addition, in this instructions, (methyl) acrylate is meant the term of general name acrylate and methacrylate, and other similarly show too.
In addition, as the compound that has 1 unsaturated group and 1 above carboxyl in 1 molecule, can list chain elongation between acrylic acid, methacrylic acid, unsaturated group and the carboxylic acid the molecule of modification unsaturated monocarboxylic ((methyl) propenoic acid beta-carboxylic ethyl ester, 2-acryloxy ethyl succinic acid, 2-acryloxy ethyl hexahydrophthalic acid, by interior unsaturated monocarboxylic with ester bond such as ester modified, have the modification unsaturated monocarboxylic of ehter bond), maleic acid etc. in comprise material of a plurality of carboxyls etc.These can use separately, also can mix multiple use.
The compound that has oxirane ring and ethylenically unsaturated group in 1 molecule preferably uses the compound that is generated by aliphatic monomer.Particularly when using the compound that generates by aliphatics polymerization monomer, can suppress the deterioration of solidfied material that the contained aromatic rings of light-cured resin causes, that cause by photoconduction, so preferably.As the compound that generates by aliphatic monomer, can list glycidyl (methyl) acrylate, Alpha-Methyl glycidyl (methyl) acrylate, 3,4-epoxy radicals cyclohexyl methyl (methyl) acrylate, 3,4-epoxy radicals cyclohexyl ethyl (methyl) acrylate, 3,4-epoxy radicals cyclohexyl butyl (methyl) acrylate, 3,4-epoxy radicals cyclohexyl methyl amino acrylates, 3,4-epoxy radicals cyclohexyl methyl (methyl) acrylate etc.The compound that has oxirane ring and ethylenically unsaturated group in 1 molecule can use separately, also can mix multiple use.
The acid number of light-cured resin need be in the scope of 50～200mgKOH/g.Under the situation of the not enough 50mgKOH/g of the acid number of light-cured resin, remove unexposed portion that the application the films difficulty that becomes with weak alkaline aqueous solution during development.In addition when the acid number of light-cured resin surpasses 200mgKOH/g, can produce the problems such as water tolerance, electric properties deteriorate of solidfied material.
In addition, the weight-average molecular weight of light-cured resin is preferably 5000～100000 scope.When the weight-average molecular weight less than 5000 of light-cured resin, there is the tendency of the remarkable variation of dry to touch that the application films.In addition, surpass at 100000 o'clock in the weight-average molecular weight of light-cured resin, so development that the application films and the remarkable variation of the storage-stable of hardening resin composition of the present invention be not preferred.
[two acylphosphine oxides are Photoepolymerizationinitiater initiater]
As two acylphosphine oxides be Photoepolymerizationinitiater initiater (below, be called " BAPO ".); can list two (2; 6-dichloro-benzoyl base) phenyl phosphine oxide; two (2,6-dichloro-benzoyl base)-2,5-3,5-dimethylphenyl phosphine oxide; two (2; 6-dichloro-benzoyl base)-4-propyl group phenyl phosphine oxide; two (2; 6-dichloro-benzoyl base)-1-naphthyl phosphine oxide; two (2,6-dimethoxy benzoyl) phenyl phosphine oxide; two (2,6-dimethoxy benzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide; two (2,6-dimethoxy benzoyl)-2,5-3,5-dimethylphenyl phosphine oxide; two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide; (2,5, the 6-trimethylbenzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide etc.Wherein, obtain two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxides (Ciba Japan K.K. system, trade name: IGRACURE 819) easily.
[the monoacyl phosphine oxide is a Photoepolymerizationinitiater initiater]
As the monoacyl phosphine oxide be Photoepolymerizationinitiater initiater (below, be called " MAPO ".); can list 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2; 6-dimethoxy benzoyl diphenyl phosphine oxide, 2; 6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl phenyl phosphinic acid methyl esters, 2-methyl benzoyl diphenyl phosphine oxide, valeryl phenyl phosphinic acid isopropyl ester etc.Wherein, obtain 2,4 easily, 6-trimethylbenzoyl diphenyl phosphine oxide (Ciba Japan K.K. system, trade name: DAROCUR TPO).
The present invention is by being used in combination BAPO and MAPO, even use filming of high reflectance that the resin combination that contains a large amount of titanium dioxide forms, also can make its curing by seeing through a spot of light of filming.Therefore, even use such resin combination and film, also can carry out the formation of the high meticulous pattern of excellent in resolution.
And, by changing the ratio that cooperates of BAPO and MAPO, photonasty that can inching hardening resin composition of the present invention.That is, in the cross sectional shape of the pattern on being formed at base material, when occurring undercutting (undercut) easily, increase the cooperation ratio of BAPO in the deep of substrate surface side curable deficiency.In addition, owing to the surface cure deficiency that the application films, during the surface state variation of the back pattern that develops, increase the cooperation ratio of MAPO.
BAPO cooperates ratio for being 90: 10～1: 99 by quality ratio, being preferably 80: 20～2: 98 with MAPO's.In the time of outside the scope of this cooperation ratio, the effect that is used in combination BAPO and MAPO diminishes, and the application films and can not obtain to solidify required light sensitivity, thereby can not form high meticulous pattern.
In addition, with respect to 100 mass parts light-cured resins, total use level of BAPO and MAPO is preferably 1～30 mass parts, 2～25 mass parts more preferably.With respect to 100 mass parts light-cured resins, under the situation of total use level less than 1 mass parts of BAPO and MAPO, the photo-curable that the application films reduces, and the pattern behind the exposure imaging forms the difficulty that becomes, so not preferred.In addition, with respect to 100 mass parts light-cured resins, total use level of BAPO and MAPO surpasses under the situation of 30 mass parts, and is big from the painted change of filming of Photoepolymerizationinitiater initiater, and then becomes the high reason of cost, so not preferred.
[titanium dioxide]
As titanium dioxide, can use any in anatase type titanium oxide, the Titanium Dioxide Rutile Top grade, be preferably Titanium Dioxide Rutile Top grade especially.Compare with Titanium Dioxide Rutile Top grade, anatase type titanium oxide is at the reflectivity height of the boundary vicinity of ultraviolet range and visible region, thus aspect whiteness and reflectivity expectation as Chinese white.Yet anatase type titanium oxide has photocatalytic activity, thereby causes the variable color of the resin of hardening resin composition sometimes owing to this photolytic activity.With respect to this, some is poor though the whiteness of Titanium Dioxide Rutile Top grade is compared with anatase type titanium oxide, does not have photolytic activity basically, thereby can suppress the deterioration of the resin of hardening resin composition of the present invention, can obtain stable solidfied material.As Titanium Dioxide Rutile Top grade, can use TIPAQUE R-820, TIPAQUE R-830, TIPAQUE R-930, TIPAQUER-550, TIPAQUE R-630, TIPAQUE R-680, TIPAQUE R-670, TIPAQUE R-780, TIPAQUE R-850, TIPAQUE CR-50, TIPAQUECR-57, TIPAQUE CR-80, TIPAQUE CR-90, TIPAQUE CR-93, TIPAQUE CR-95, TIPAQUE CR-97, TIPAQUE CR-60, TIPAQUECR-63, TIPAQUE CR-67, TIPAQUE CR-58, TIPAQUE CR-85, TIPAQUE UT771 (the former industry of stone (strain) system), Ti-Pure R-100, Ti-PureR-101, Ti-Pure R-102, Ti-Pure R-103, Ti-Pure R-104, Ti-PureR-105, Ti-Pure R-108, Ti-Pure R-900, Ti-Pure R-902, Ti-PureR-960, Ti-Pure R-706, Ti-Pure R-931 (Du Pont Kabushiki Kaisha system), TIT ON R-25, TIT ON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300, TITON D-918, TITON TCR-29, TITONTCR-52, TITON FTR-700 (Sakai chemical industry (strain) system) etc.
In addition, as anatase type titanium oxide, can list TA-100, TA-200, TA-300, TA-400, TA-500 (Fuji Titanium Industry Co., the Ltd system), TIPAQUE A-100, TIPAQUE A-220, TIPAQUE W-10 (the former industry of stone (strain) system), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5 (TAYCA CORPORATION system), KRONOS KA-10, KRONOS KA-15, KRONOS KA-20, KRONOS KA-30 (Titan Kogyo, Ltd. system), A-100, SA-1, SA-1L (Sakai chemical industry (strain) system) etc.
With respect to composition (comprising titanium dioxide) 100 mass parts beyond the organic solvent of solidification compound of the present invention, the use level of titanium dioxide is 40～80 mass parts.Even in this resin combination, cooperate the titanium dioxide of the scope that surpasses above-mentioned use level, this resin combination, the application film and the reflectivity of solidfied material can significantly not improve yet, and then in the case, the photo-curable of this resin combination reduces, so the curing depth step-down is not preferred.On the other hand, with respect to the composition beyond the organic solvent of solidification compound of the present invention, during use level less than 40 mass parts of titanium dioxide, the power of covering of this resin combination diminishes, and is difficult to obtain the solidfied material of high reflectance, so not preferred.
[organic solvent]
Organic solvent is used to that hardening resin composition of the present invention is in and is easy to the state that is coated with to base material etc. and this resin combination that will contain organic solvent and coats base material etc., makes it dry and form and film.As organic solvent, can list ketones such as MEK, cyclohexanone; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, TC, dihydroxypropane single-ethyl ether, triethylene glycol list ethylether; The ester classes such as carboxylate of ethyl acetate, butyl acetate, cellosolve acetic acid esters, TC acetic acid esters and above-mentioned glycol ethers; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.
Organic solvent can use separately or as a plurality of potpourris.With respect to 100 mass parts light-cured resins, the use level of organic solvent is preferably 20～300 mass parts.
[urethane acrylate]
In hardening resin composition of the present invention, can cooperate urethane acrylate.Urethane acrylate mainly cooperates for following purpose.The first is used to improve the adaptation of solidfied material and this base material, so that hardening resin composition of the present invention can be used in difficult cementability thermoplastic matrix.Another purpose is, cooperating in hardening resin composition of the present invention for solidfied material being given stable on heating purpose under the situation of epoxy compound and antioxidant, be used to improve solidfied material flexible, make solidfied material can follow the bending of base material in addition have flexible base material so that this resin combination can be used in.
As this urethane acrylate, can use CN929, CN940, CN944B85, CN959, CN961H81, CN962, CN963A80, CN963B80, CN963E75, CN963E80, CN963J75, CN964, CN964A85, CN964E75, CN965, CN965A80, CN966A80, CN966B85, CN966H90, CN966J75, CN966R60, CN968, CN980, CN981, CN981A75, CN981B88, CN982A75, CN982B88, CN982E75, CN982P90, CN983, CN985B88, CN989, CN991, CN996, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9014, CN9178, CN9788, CN9893 (Sartomer corporate system), M-1100, M-1200, M-1210, M-1600 (East Asia synthetic (strain) system), U-2PPA, U-4HA, U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, UA-NDP, U-4H, U-6H, U-108A, U-200AX, UA-511, U-412A, UA-4100, UA-4200, UA-4400, UA-340P, UA-2235PE, UA-3458P, UA-160TM, UA-6100, UA-6200U-108, UA-4000, UA-122P, UA-5201, UA-512, UA-6373P (Xin Zhong village chemical industry (strain) system) etc.
With respect to 100 mass parts light-cured resins, the use level of urethane acrylate is preferably 10～100 mass parts, 20～80 mass parts more preferably.With respect to 100 mass parts light-cured resins, when the use level of urethane acrylate surpassed 100 mass parts, the rerum natura of solidfied material reduced, so not preferred.On the other hand, with respect to 100 mass parts light-cured resins, during use level less than 10 mass parts of urethane acrylate, solidfied material can not obtain sufficient adaptation or flexible, so not preferred.
[epoxy compound]
Requiring solidfied material to have under the stable on heating situation,, can in hardening resin composition of the present invention, cooperate epoxy compound for solidfied material being given stable on heating purpose.As epoxy compound, can list bisphenol-s epoxy resin, the diglycidyl phthalate resin, triglycidyl group isocyanuric acid ester (TEPIC-H (the β body of daily output chemical industry (strain) system, have with respect to 3 epoxy radicals structures that bonding forms on same direction of s-triazine ring skeleton face), TEPIC (potpourri of β body and α body, α body have with respect to 1 epoxy radicals of s-triazine ring skeleton face structure that bonding forms on the direction different with other 2 epoxy radicals) etc.) hetero ring type epoxy resin such as, di-toluene phenol-type epoxy resin, biphenyl type epoxy resin, four glycidyl group xylenols ethane resin etc. is the epoxy resin of slightly solubility in thinning agent, bisphenol A type epoxy resin, bisphenol-A epoxy resin, Bisphenol F type resin, brominated bisphenol a type epoxy resin, phenol phenolic varnish type or cresols phenolic resin varnish type epoxy resin, alicyclic epoxy resin, the phenolic resin varnish type epoxy resin of bisphenol-A, chelate type epoxy resin, glyoxal type epoxy resin, contain aminoepoxy resin, rubber modified epoxy resin, the bicyclopentadiene phenol aldehyde type epoxy resin, modifying epoxy resin by organosilicon, 6-caprolactone modified epoxies etc. are the epoxy resin of solubility etc. in thinning agent.These epoxy resin can use or make up multiple use separately.
Cooperate in hardening resin composition of the present invention under the situation of epoxy compound, with respect to 100 mass parts light-cured resins, its use level is preferably 5～70 mass parts, 5～60 mass parts more preferably.With respect to 100 mass parts light-cured resins, when the use level of epoxy compound surpassed 70 mass parts, the dissolubility of unexposed portion in developer solution reduced for the application films, and it is residual to take place easily to develop, thereby is difficult to carry out the formation of pattern.On the other hand, with respect to 100 mass parts light-cured resins, during use level less than 5 mass parts of epoxy compound, the carboxyl of light-cured resin remains in the solidfied material with unreacted state, thereby is difficult to fully obtain the electrical characteristics of solidfied material, anti-sweating heat performance, chemical proofing.
In addition, under situation about epoxy compound being coupled in the hardening resin composition of the present invention, the carboxyl of light-cured resin and the epoxy radicals of epoxy compound are reacted by ring-opening polymerization.And in the case, when other materials to organic solvent, this resin combination are the epoxy resin of ease of solubility when also being coupled in this resin combination, the hot above-mentioned carboxyl of the drying when filming by forming the application and crosslinked the becoming of epoxy radicals are carried out easily.Therefore, plan to suppress this cross-linking reaction and prolonging under the situation of drying time, expectation be that cooperating other materials to organic solvent, this resin combination separately is the epoxy resin of slightly solubility, or cooperates with the epoxy resin of ease of solubility.
[antioxidant]
Epoxy compound is being matched with under the situation of hardening resin composition of the present invention, can antioxidant be matched with this resin combination for the purpose of the variable color that hot deterioration caused that reduces solidfied material.As antioxidant, be preferably the hindered phenol based compound, but be not limited to these.As the hindered phenol based compound, can list NOCRAC 200, NOCRAC M-17, NOCRAC SP, NOCRAC SP-N, NOCRAC NS-5, NOCRAC NS-6, NOCRAC NS-30, NOCRAC300, NOCRAC NS-7, NOCRAC DAH (more than be the emerging chemical industry of imperial palace (strain) system); MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (more than be Adeka Argus Chemical Co., the Ltd. system); IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX 1010, IRGANOX1035, IRGANOX 1076, IRGANOX 1081, IRGANOX 1098, IRGANOX 1222, IRGANOX 1330, IRGANOX 1425WL (more than be Ciba Japan K.K. system) etc.
Under situation about antioxidant being coupled in the hardening resin composition of the present invention, with respect to 100 mass parts light-cured resins, its use level is preferably 0.4～25 mass parts, 0.8～15 mass parts more preferably.With respect to 100 mass parts light-cured resins, under the situation of use level less than 0.4 mass parts of antioxidant, prevent that the effect of the variable color that hot deterioration causes of solidfied material from diminishing.In addition, with respect to 100 mass parts light-cured resins, the use level of antioxidant surpasses under the situation of 25 mass parts, and the development reduction that this is filmed is unsuitable for patterning.
In addition, for the purpose of the dispersiveness of improving titanium dioxide, settleability, can cooperate spreading agent in the hardening resin composition of the present invention.As spreading agent, can list ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (BYK Japan KK system), DISPARLON 2150, DISPARLON1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850, DISPARLON DA-400N, DISPARLONPW-36, DISPARLON DA-703-50 (nanmu originally changes into (strain) system), FLOWLENG-450, FLOWLEN G-600, FLOWLEN G-820, FLOWLEN G-700, FLOWLEN DOPA-44, FLOWLEN DOPA-17 (common prosperity society chemistry (strain) system) etc.
In order to achieve the above object, with respect to 100 mass parts titanium dioxide, the use level of spreading agent can be for 0.1～10 mass parts, be preferably 0.5～5 mass parts.
And then can also cooperate hindered amine for the purpose that reduces the light deterioration in hardening resin composition of the present invention is light stabilizer.
As this hindered amine is light stabilizer, can list TINUVIN 622LD, TINUVIN 144; CHIMASSORB 944LD, CHIMASSORB 119FL (more than be Ciba Japan K.K. system); MARK LA-57, LA-62, LA-67, LA-63, LA-68 (more than be Adeka Argus Chemical Co., the Ltd. system); Sanol LS-770, LS-765, LS-292, LS-2626, LS-1114, LS-744 (more than be Sankyo Life Tech Co., the Ltd. system) etc.
With respect to 100 mass parts light-cured resins, hindered amine is that the use level of light stabilizer is preferably 0.1～10 mass parts.
Can also cooperate the thioxanthones as Photoepolymerizationinitiater initiater in hardening resin composition of the present invention is Photoepolymerizationinitiater initiater.The sensitivity of the light in the time of thus, can improving hardening resin composition of the present invention to exposure.As thioxanthones is Photoepolymerizationinitiater initiater, can list thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.
In addition, in hardening resin composition of the present invention, can also cooperate photopolymerization sensitizer, polymerization inhibitor, tackifier, defoamer, levelling agent, coupling agent, flame retardants etc. such as thioxanthones system.
(use of composition)
Below, as the use-case that makes of hardening resin composition of the present invention, describe for the reflector plate that uses this resin combination manufacturing.
(making use-case 1)
In the hardening resin composition of the present invention; to comprise 1 molecule contain the resin of ethylenically unsaturated group and carboxyl and two acylphosphine oxide be Photoepolymerizationinitiater initiater and monoacyl phosphine oxide be Photoepolymerizationinitiater initiater and titanium dioxide and organic solvent and urethane acrylate hardening resin composition (below, be called " composition 1 ".) adjust to the viscosity that is fit to coating process.
Then, the composition 1 that will adjust after the viscosity of the method that is coated with method, spraying process or rolling method etc. by silk screen print method, curtain formula is coated difficult cementability thermoplastic matrixes such as polyester base material.Then, under 70～90 ℃ temperature, make the contained organic solvent volatile dry of composition 1 of coating base material, form and film (below, be called " filming 1 ".)。
Then, 1 carry out selectivity exposure by active energy beam to filming across photomask.And 1 the unexposed portion of filming after using alkaline aqueous solution to exposure develops, and forms circuit pattern, can make reflector plate of the present invention thus.
In the case, as difficult cementability thermoplastic matrix, can list ethylene series base material, polyamide-based base material, polyester is base material etc.As the ethylene series base material, can list high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), polypropylene (PP), cyclic olefin polymer etc.As polyamide-based base material, can list nylon 6, nylon 11, nylon 12, nylon 66, nylon 612, nylon 6T, NYLON610 etc.As polyester is base material, can list polyethylene terephthalate (PET), PEN (PEN), PTT (PTT), polybutylene terephthalate (PBT), PBN (PBN) etc.As other base materials, can list Vingon, polytetrafluoroethylene (PTFE), polyacetal (POM), polyphenylene oxide (PPE), polyphenylene sulfide (PPS) etc.
(making use-case 2)
In the hardening resin composition of the present invention; to comprise 1 molecule contain the resin of ethylenically unsaturated group and carboxyl and two acylphosphine oxide be Photoepolymerizationinitiater initiater and monoacyl phosphine oxide be Photoepolymerizationinitiater initiater and titanium dioxide and organic solvent and urethane acrylate and epoxy compound and antioxidant hardening resin composition (below, be called " composition 2 ".) adjust to the viscosity that is fit to coating process.
Then, being coated with methods such as method, spraying process or rolling method by silk screen print method, curtain formula will adjust composition 2 after the viscosity and coat and have on the flexible base material.Then, under 70～90 ℃ temperature, make the contained organic solvent volatile dry of composition 2 of coating base material, form and film (below, be called " filming 2 ".)。
Then, 2 carry out selectivity exposure by active energy beam to filming across photomask.And 2 the unexposed portion of filming after using alkaline aqueous solution to exposure develops, and forms pattern.And then, carry out heat curing by pattern under 100 ℃～200 ℃ temperature to this formation, can make reflector plate of the present invention thus.
In the case, as having flexible base material, can list Apical AH, Apical NPI (KANEKA CORPORATION system), Kapton H, Kapton V, Kapton EN (DU PONT-TORAY CO., LTD. system), UPILEX 25S, UPILEX 75S metal formings such as Kapton, Copper Foil, aluminium foil, stainless steel foil, titanium foil, nickel foil such as (the emerging product of space portion (strain) systems) etc.
In addition, film 1 and 2 the radiation source of filming as being used to expose, can use low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp or metal halide lamp etc.In addition, laser beam etc. also can be used as active ray.
In addition,, be generally the aqueous sodium carbonate of 0.5～5 quality %, also can use other alkaline aqueous solutions as being used to film 1 and the alkaline aqueous solution of 2 developer solutions that develop of filming.As other alkaline aqueous solutions, can list the alkaline aqueous solution of potassium hydroxide, NaOH, sal tartari, sodium phosphate, sodium silicate, ammonium, amine etc.
Embodiment
Embodiment and comparative example below are shown come the present invention is specifically described, but the present invention is not limited to following embodiment.
Synthesizing of resin solution 1:
In 2 liters of removable flasks that possess stirring machine, thermometer, reflux condenser, tap funnel and nitrogen ingress pipe, add 900g solvent (diethylene glycol dimethyl ether) and 21.4g polymerization initiator (tert-butyl hydroperoxide 2 ethyl hexanoic acid ester, Japanese grease (strain) system, trade name: Perbutyl O), be heated to 90 ℃.After the heating, PLACCEL FMl) and 21.4g polymerization initiator (two (4-tert-butylcyclohexyl) peroxy dicarbonate, Japanese grease (strain) system, trade name: PEROYL TCP) with in above-mentioned flask, being added dropwise to 309.9g methacrylic acid, 116.4g methyl methacrylate, 109.8g lactone modified methacrylic acid 2-hydroxyl ethyl ester (DAICELCHEMICAL INDUSTRIES, LTD. system, trade name: in 3 hours.Further by this potpourri is carried out 6 hours aging, thereby obtain to contain the carboxyl copolymer resins.In addition, these are reflected under the nitrogen atmosphere and carry out.
Then, contain adding 363.9g 3 in the carboxyl copolymer resins to this, 4-epoxy radicals cyclohexyl methyl acrylate (DAICEL CHEMICAL INDUSTRIES, CYCLOMER A200), 3.6g ring opening catalyst (dimethyl benzyl amine), 1.80g polymerization inhibitor (Hydroquinone monomethylether) LTD. system, trade name:, these are heated to 100 ℃, stir, thereby carry out the opening of epoxy radicals.Stir to stop after 16 hours, stir thing by this and obtain solution, the acid number that this solution comprises solid constituent be 108.9mgKOH/g, weight-average molecular weight be 25000 do not have an aromatic rings contain carboxy resin 53.8 quality % (nonvolatile component).Below, this reaction solution is called resin solution 1.
(embodiment (1))
The making of each hardening resin composition (embodiment 1～3, comparative example 1～6):
Stirring further disperses it by three roller roller mills by the potpourri that the record of table 1 cooperates each composition to form, and makes hardening resin composition (embodiment 1～3, comparative example 1～6).In addition, comparative example 1 is represented the composition that the use level of titanium dioxide is lacked than regulation use level of the present invention, the composition that the use level of comparative example 2 expression titanium dioxide is Duoed than regulation use level of the present invention, comparative example 3 expressions only are combined with the composition of BAPO as Photoepolymerizationinitiater initiater, comparative example 4 expressions only are combined with the composition of MAPO as Photoepolymerizationinitiater initiater, comparative example 5 expressions are combined with the composition of the Photoepolymerizationinitiater initiater except that BAPO and MAPO as Photoepolymerizationinitiater initiater, comparative example 6 expression replaces urethane acrylates and cooperates the composition of photopolymerization monomer.In addition, the numeral mass parts in the table 1.
[table 1]
Figure BDA0000064494650000231
Photoepolymerizationinitiater initiater 1 (BAPO): two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide IGRACURE 819 (Ciba Japan K.K. system)
Photoepolymerizationinitiater initiater 2 (MAPO): 2,4,6-trimethylbenzoyl diphenyl phosphine oxide DAROCUR TPO (Ciba Japan K.K. system)
Photoepolymerizationinitiater initiater 3:IGRACURE 907 (Ciba Japan K.K. system)
Urethane acrylate: CN9178 (Sartomer corporate system)
Photopolymerization monomer: dipentaerythritol acrylate
Titanium dioxide (rutile-type): CR-Super70 (the former industry of stone (strain) system)
Sensitizer: 2,4-diethyl thioxanthone Kayacure DETX-S (Japanese chemical drug (strain) system)
Organic solvent: carbitol acetic acid esters
Defoamer: organic silicone oil KS-66 (SHIN-ETSU HANTOTAI's chemical industry (strain) system)
In order to investigate each character of the solidfied material that uses each hardening resin composition formation, test by following condition, and estimate.
(1) resolution
Use 100 order polyester (twill system) versions, by silk screen print method with each hardening resin composition be printed in to have one's face covered with PET (size: 100mm * 150mm, thickness: 100 μ m) so that its thickness of filming is 60 μ m.Make this PET drying (temperature: 80 ℃, time: 20 minutes) by the heated air circulation type drying oven then, form filming of above-mentioned each resin combination.And then, with exposure machine HMW-680GW (ORCMANUFAC TURING CO., LTD. system), use the mask pattern of the removal molded lines of the line of describing 80 μ m and 50 μ m, with 700mJ/cm 2The accumulative total light quantity above-mentioned respectively filming carried out ultraviolet exposure.Then, to respectively filming after this exposure, the aqueous sodium carbonate (temperature: 30 ℃) that uses 1 quality % uses developing machine to carry out for 60 seconds and develops as developer solution, makes each test film.
Confirm this test film, use following evaluation method to carry out the evaluation of resolution.It the results are shown in table 2.
Zero mask pattern is residual to have the line of 80 μ m or the removal molded lines of 50 μ m to remove
* heading line off or removal owing to halation owing to develop
(2) adaptation
Use 100 order polyester (twill system) versions, by silk screen print method with each hardening resin composition be printed in to have one's face covered with PET (size: 100mm * 150mm, thickness: 100 μ m) so that its thickness of filming is 60 μ m.Make this PET drying (temperature: 80 ℃, time: 20 minutes) by the heated air circulation type drying oven then, form filming of above-mentioned each resin combination.And then, use exposure machine HMW-680GW (ORCMANUFACTURING CO., LTD. system), with 700mJ/cm 2The accumulative total light quantity above-mentioned respectively filming carried out ultraviolet exposure so that the negative pattern of the square minus of residual 80mm.Then, for respectively filming after this exposure, the aqueous sodium carbonate (temperature: 30 ℃) that uses 1 quality % uses developing machine to carry out for 60 seconds and develops as developer solution, makes each test film.
After these test films being wound up into the cylinder of diameter 1cm, length 20cm, revert to plane once more.The cured coating film of observing each test film at this moment is (in embodiment (1), hereinafter referred to as " filming ".) state, use following evaluation method to estimate adaptation.It the results are shown in table 2.
Zero films does not have state variation
The part that △ films is peeled off
* film and peel off comprehensively, almost do not have residual
(3) reflectivity
Use the method making test film same,, obtain reflectivity with the Y value that color colour difference meter CR-400 (Konica Minolta Sensing, Inc. system) measures the XYZ colorimetric system of each test film with (2).In addition, in the present embodiment, supposing the situation that improves the brightness of LED etc. as reflecting plate, is qualified more than 75 with the Y value.
It the results are shown in table 2.As shown in table 2, except comparative example 1, all obtain the Y value and be the filming of high reflectance more than 75.
Figure BDA0000064494650000261
(4) photostability
For embodiment 1 to 3, use the method making test film same with (3), each value of measuring the Y value of XYZ colorimetric system of each test film and L*a*b* colorimetric system with color colour difference meter CR-400 (Konica Minolta Sensing, Inc. system) is as initial value.Then, use conveying type UV irradiating machine QRM-2082-E-01 ((strain) ORCMANUFACTURING CO., LTD. system), with metal halide lamp, cold mirror, 80W/cm * 3 lamps, transporting velocity 6.5m/ minute (accumulative total light quantity 1000mJ/cm 2) condition, to above-mentioned each test film irradiation UV, 100 times repeatedly.And then, above-mentioned each test film with the condition mensuration aberration same with initial value, is estimated the deterioration state of each test film.In addition, this each test film of visual valuation.
In the table 3, Y represents the reflectivity of XYZ colorimetric system, and L* represents the brightness of L*a*b* colorimetric system.△ E*ab is following value: for each value of L*a*b*, get the quadratic power of the difference of measured value after the deterioration test and initial value, ask the square root of its summation.A* represent red direction ,-a* represent green direction, b* represent yellow direction ,-b* represents blue direction, do not have colourity more near null representation more.△ E*ab represents change in color.The more little expression change in color of this value is more little.
In addition, the visual valuation project is as described below.
Zero does not feel variable color
△ has variable color slightly
* tangible variable color arranged
As table 3 was put down in writing, solidfied material was considerably less by the variable color that UV causes for embodiment 1～3 as can be known.
[table 3]
Figure BDA0000064494650000281
As known from the above, according to present embodiment, can obtain following hardening resin composition: it can form the solidfied material that can obtain sufficient adaptation and light also be had the high reflectance of good anti-deterioration difficult cementability thermoplastic matrixes such as polyester.In addition, also this resin combination can form high meticulous pattern by exposure as can be known, has good resolution.
(embodiment (2))
The making of each hardening resin composition (embodiment 4～6, comparative example 7～13):
Stirring further disperses it with three roller roller mills according to the potpourri that the record of table 4 cooperates each composition to form, and makes hardening resin composition (embodiment 4～6, comparative example 7～13).In addition, comparative example 7 expressions do not cooperate the composition of antioxidant, comparative example 8 expressions replace urethane acrylate to be combined with the composition of photopolymerization monomer, the composition that the use level of comparative example 9 expression titanium dioxide is lacked than regulation use level of the present invention, the composition that the use level of comparative example 10 expression titanium dioxide is Duoed than the use level of the present invention's regulation, comparative example 11 expressions only are combined with the composition of BAPO as Photoepolymerizationinitiater initiater, comparative example 12 expressions only are combined with the composition of MAPO as Photoepolymerizationinitiater initiater, comparative example 13 expressions are combined with the composition of the Photoepolymerizationinitiater initiater except that BAPO and MAPO as Photoepolymerizationinitiater initiater.In addition, the numeral mass parts in the table 4.
[table 4]
Photoepolymerizationinitiater initiater 1 (BAPO): two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide IGRACURE 819 (Ciba Japan K.K. system)
Photoepolymerizationinitiater initiater 2 (MAPO): 2,4,6-trimethylbenzoyl diphenyl phosphine oxide DAROCUR TPO (Ciba Japan K.K. system)
Photoepolymerizationinitiater initiater 3:IGRACURE 907 (Ciba Japan K.K. system)
Urethane acrylate: CN9178 (Sartomer corporate system)
Photopolymerization monomer: dipentaerythritol acrylate
Titanium dioxide (rutile-type): CR-Super70 (the former industry of stone (strain) system)
Epoxy compound (biphenyl type): YX-4000 (Japan Epoxy ResinsCo., Ltd. system)
Antioxidant: IRGANOX 1010 (Ciba Japan K.K. system)
Defoamer: organic silicone oil KS-66 (SHIN-ETSU HANTOTAI's chemical industry (strain) system)
Organic solvent: carbitol acetic acid esters
In order to investigate each character of the solidfied material that uses each hardening resin composition formation, test by following condition, and estimate.
(1) resolution
Use 100 order polyester (twill system) versions, by silk screen print method with each hardening resin composition be printed in to have one's face covered with aluminium foil (size: 100mm * 150mm, thickness: 150 μ m) so that its thickness of filming is 60 μ m.Then, use the heated air circulation type drying oven to make this aluminium foil drying (temperature: 80 ℃, time: 20 minutes), form filming of above-mentioned each resin combination.And then, with exposure machine HMW-680GW (ORCMANUFACTURING CO., LTD. system), use the mask pattern of the line of describing 80 μ m, with 700mJ/cm 2The accumulative total light quantity above-mentioned respectively filming carried out ultraviolet exposure.Then, to respectively filming after this exposure, the aqueous sodium carbonate (temperature: 30 ℃) that uses 1 quality % uses developing machine to carry out for 60 seconds and develops as developer solution.Then, use heated air circulation type drying oven (temperature: 150 ℃, time: 60 minutes) that respectively filming after developing carried out heat curing, make each test film.
Affirmation residual line width on these test films uses following evaluation method to estimate.It the results are shown in table 5.
Zero line is residual
* line is not residual
(2) flexible
Use 100 order polyester (twill system) versions, by silk screen print method with each hardening resin composition be printed in to have one's face covered with aluminium foil (size: 100mm * 150mm, thickness: 150 μ m) so that its thickness of filming is 60 μ m.Then, use the heated air circulation type drying oven to make this aluminium foil drying (temperature: 80 ℃, time: 20 minutes), form filming of above-mentioned each resin combination.And then, use exposure machine HMW-680GW (ORC MANUFACTURING CO., LTD. system), with 700mJ/cm 2The accumulative total light quantity above-mentioned respectively filming carried out ultraviolet exposure so that the negative pattern of the square minus of residual 80mm.Then, to respectively filming after this exposure, the aqueous sodium carbonate (temperature: 30 ℃) that uses 1 quality % uses developing machine to carry out for 60 seconds and develops as developer solution.Then, use heated air circulation type drying oven (temperature: 150 ℃, time: 60 minutes) that respectively filming after developing carried out heat curing, make each test film.
These test films are wound up into the cylinder of diameter 2cm, length 20cm, and the cured coating film of observing this moment is (in embodiment (2), hereinafter referred to as " filming ".) state, use following evaluation method to estimate to flexible.It the results are shown in table 5.
Zero films does not have crackle fully, and state does not change
△ films crackle slightly
* tangible the crackle of having filmed
(3) reflectivity
Use the method making test film same,, obtain reflectivity with the Y value that color colour difference meter CR-400 (Konica Minolta Sensing, Inc. system) measures the XYZ colorimetric system of each test film with (2).In addition, in the present embodiment, supposing the situation that improves the brightness of LED etc. as reflecting plate, is qualified more than 75 with the Y value.
It the results are shown in table 5.As table 5 is put down in writing,, obtain the Y value and be the filming of high reflectance more than 75 except comparative example 9.
[table 5]
(4) fast light thermotolerance
For embodiment 4 to 6 and comparative example 7, use the method making test film same with (3), each value of measuring the Y value of XYZ colorimetric system of each test film and L*a*b* colorimetric system with color colour difference meter CR-400 (Konica Minolta Sensing, Inc. system) is as initial value.Then, use conveying type UV irradiating machine QRM-2082-E-01 (ORC MANUFACTURING CO., LTD. system), with metal halide lamp, cold mirror, 80W/cm * 3 lamps, transporting velocity 6.5m/ minute (accumulative total light quantity 1000mJ/cm 2) condition, to above-mentioned each test film irradiation UV, 20 times repeatedly.And then use the conveying-type heating furnace this each test film to be heated twice repeatedly.Then,, this each test film is measured aberration, estimate the deterioration state of each test film with the condition same with initial value.In addition, this each test film of visual valuation.It the results are shown in table 6.In addition, Fig. 1 represents the heating-up temperature of heating furnace.
In the table 6, Y represents the reflectivity of XYZ colorimetric system, and L* represents the brightness of L*a*b* colorimetric system.△ E*ab is following value: for each value of L*a*b*, get the quadratic power of the difference of measured value after the deterioration test and initial value, ask the square root of its summation.A* represent red direction ,-a* represent green direction, b* represent yellow direction ,-b* represents blue direction, do not have colourity more near null representation more.△ E*ab represents change in color.The more little expression change in color of this value is more little.
In addition, the visual valuation project is as described below.
Zero does not almost have variable color
△ has variable color slightly
* obvious variable color arranged
As table 6 is put down in writing, to embodiment 4 to 6, almost be not visually observed deterioration, it is high reflectance more than 75 that reflectivity also remains on the Y value.On the other hand, do not contain in the comparative example 7 of antioxidant and observe tangible xanthochromia, the reduction of reflectivity also is significant in addition.
[table 6]
Figure BDA0000064494650000361
(5) anti-sweating heat performance
For embodiment 4 to 6, the rosin series solder flux is coated each test film by making with (2) same method, make it in 260 ℃ solder bath, flow through for 10 seconds.Then, wash this each test film, make its drying with propylene glycol monomethyl ether.Then,, carry out disbonded test, use following evaluation method that peeling off of filming estimated with the viscose paper adhesive strip for dried each test film.It the results are shown in table 7.
Zero do not film peel off
* peeling off of filming arranged
(6) solvent resistance
For embodiment 4 to 6, will use each test film made from (2) same method in propylene glycol monomethyl ether, to flood 30 minutes, make its drying.Then,, carry out disbonded test, use following evaluation method that peeling off with variable color of filming estimated with the viscose paper adhesive strip for dried each test film.It the results are shown in table 7.
Zero do not film peel off, variable color
* peeling off of filming, variable color arranged
(7) insulation resistance test
For embodiment 4 to 6, replace aluminium foil, to the comb-type electrode B test pieces that FR-4 uses IPC B-25 test pattern, in addition, use condition and the method making test film same with (2).This each test film is applied the bias voltage of DC500V, measure insulating resistance value.It the results are shown in table 7.
[table 7]
Figure BDA0000064494650000381
As known from the above, according to present embodiment, can access following hardening resin composition: it can be formed on having flexible base material, and the Y value is the solidfied material of the high reflectance more than 75 in the XYZ colorimetric system.In addition, also as can be known this resin combination can form high meticulous pattern, have good resolution by exposure.And then, use the deterioration that causes by light, thermal conductance of the solidfied material that above-mentioned resin combination forms few, also have anti-sweating heat performance.
Utilizability on the industry
As mentioned above, the present invention relates to employed hardening resin compositions such as reflector plate, reflecting plate for the light of reflection LED etc.
And, according to the present invention, also can be at the pattern of the formation excellent in resolution such as reflector plate even contain a large amount of titanium oxide.
In addition, by in this resin combination, cooperating urethane acrylate, even contain a large amount of titanium oxide, also can form excellent in resolution and to the pattern of the adaptation excellence of this base material in the bonding plastic substrate hot in nature of difficulty.
And then the present invention is by cooperating urethane acrylate, epoxide and antioxidant in above-mentioned resin combination, also can have flexible base material and form the pattern of excellent in resolution and excellent heat resistance even contain a large amount of titanium oxide.
Therefore in the present invention, can in various uses, utilize these reflector plates, reflecting plate etc.

Claims (13)

1. hardening resin composition, it comprises:
1 molecule contain ethylenically unsaturated group and carboxyl resin and
Two acylphosphine oxides be Photoepolymerizationinitiater initiater and
The monoacyl phosphine oxide be Photoepolymerizationinitiater initiater and
Titanium dioxide and
Organic solvent.
2. hardening resin composition is characterized in that it comprises:
1 molecule contain ethylenically unsaturated group and carboxyl resin and
Two acylphosphine oxides be Photoepolymerizationinitiater initiater and
The monoacyl phosphine oxide be Photoepolymerizationinitiater initiater and
Organic solvent and
With respect to 100 mass parts of the composition except that organic solvent is the titanium dioxide of 40～80 mass parts.
3. according to claim 1 or the described hardening resin composition of claim 2, it is characterized in that titanium dioxide is a Titanium Dioxide Rutile Top grade.
4. according to claim 1 or the described hardening resin composition of claim 2, it is characterized in that the resin that 1 molecule contains ethylenically unsaturated group and carboxyl is a resin for the copolymerization with carboxyl that contains the compound reaction that has oxirane ring and ethylenically unsaturated group in carboxyl (methyl) acrylic acid series copolymer resins and 1 molecule and obtain.
5. hardening resin composition according to claim 4 is characterized in that, has the compound of compound for being generated by aliphatics polymerization monomer of oxirane ring and ethylenically unsaturated group in 1 molecule.
6. according to claim 1 or the described hardening resin composition of claim 2, it is characterized in that it comprises urethane acrylate.
7. according to claim 1 or the described hardening resin composition of claim 2, it is characterized in that it comprises epoxy compound and antioxidant.
8. according to claim 1 or the described hardening resin composition of claim 2, it is characterized in that it comprises epoxy compound and antioxidant and urethane acrylate.
9. reflector plate, its solidfied material by claim 1 or the described hardening resin composition of claim 2 forms.
10. reflector plate, it is formed by difficult cementability thermoplastic matrix and the solidfied material that is arranged at the described hardening resin composition of claim 6 of this base material.
11. a reflector plate, its solidfied material by the described solidification compound of claim 7 forms.
12. a reflector plate, it is formed by the solidfied material that has flexible base material and be arranged at the described hardening resin composition of claim 8 of this base material.
13. a reflector plate is characterized in that, it is formed by base material and the solidfied material that is arranged at the hardening resin composition of this base material, wherein,
This solidfied material comprises:
Have ethylenically unsaturated group compound and
Two acylphosphine oxides be Photoepolymerizationinitiater initiater and
The monoacyl phosphine oxide be Photoepolymerizationinitiater initiater and
Titanium dioxide.
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6061440B2 (en) * 2010-02-25 2017-01-18 太陽ホールディングス株式会社 Resin composition for polyester substrate, dry film and printed wiring board using the same
JP5636209B2 (en) * 2010-04-23 2014-12-03 太陽ホールディングス株式会社 Solder resist composition and printed wiring board
JP5650460B2 (en) * 2010-08-18 2015-01-07 株式会社タムラ製作所 White curable resin composition
WO2012111356A1 (en) * 2011-02-14 2012-08-23 積水化学工業株式会社 Two-liquid mixing first and second liquids and method for producing printed circuit board
JP5967462B2 (en) * 2011-06-22 2016-08-10 大日本印刷株式会社 Louver seat
JP5971977B2 (en) * 2012-02-24 2016-08-17 株式会社タムラ製作所 White curable resin composition
JP6153368B2 (en) * 2013-03-31 2017-06-28 株式会社村上開明堂 Colored anti-fog mirror for vehicle outer mirror
JP5968291B2 (en) 2013-09-30 2016-08-10 太陽インキ製造株式会社 White curable composition for printed wiring board, cured coating film using the same, and printed wiring board
JP5876862B2 (en) * 2013-12-03 2016-03-02 太陽ホールディングス株式会社 Resin composition for polyester substrate, dry film and printed wiring board using the same
JP5990291B2 (en) * 2014-04-11 2016-09-14 太陽インキ製造株式会社 Photosensitive resin composition, dry film, cured product, and printed wiring board
US10323154B2 (en) * 2015-02-11 2019-06-18 Xerox Corporation White ink composition for ink-based digital printing
DE102017201991A1 (en) * 2017-02-08 2018-08-09 Lufthansa Technik Ag Embossing lacquer composition, microstructured surface produced therefrom and aircraft component having such a microstructured surface

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09183920A (en) * 1995-12-28 1997-07-15 Puresuteeji:Kk Ultraviolet-curing resin composition for formation of light-reflecting portion, light-reflecting portion made of cured coating film of said composition, and backlight unit made by using the same
DE19812859A1 (en) * 1998-03-24 1999-09-30 Basf Ag Mixtures of photoinitiators
SE9904080D0 (en) * 1998-12-03 1999-11-11 Ciba Sc Holding Ag Fotoinitiatorberedning
KR100685153B1 (en) * 1998-12-03 2007-02-22 시바 스페셜티 케미칼스 홀딩 인크. Photoinitiator combinations, compositions comprising those combinations and their use
JP2004318047A (en) * 2003-03-31 2004-11-11 Sumitomo Bakelite Co Ltd Photosensitive resin composition, laminate, wiring board, and flexible wiring board
JP4410054B2 (en) * 2004-07-30 2010-02-03 出光興産株式会社 Light reflecting sheet and molded product thereof
JP2006235101A (en) * 2005-02-23 2006-09-07 Fuji Photo Film Co Ltd Photosensitive composition, photosensitive film, permanent pattern and method for forming the same
JP4711208B2 (en) * 2006-03-17 2011-06-29 山栄化学株式会社 Photosensitive thermosetting resin composition, resist film-coated smoothed printed wiring board, and method for producing the same.
JP2007256669A (en) * 2006-03-23 2007-10-04 Fujifilm Corp Photosensitive film, method for forming permanent pattern and printed circuit board
JP4340272B2 (en) * 2006-05-30 2009-10-07 太陽インキ製造株式会社 Photocurable / thermosetting solder resist composition and printed wiring board using the same
KR100800463B1 (en) * 2006-08-08 2008-02-04 엘지전자 주식회사 Paste composition for dielectric layer, plasma display panel using the same and manufacturing method thereof
JP4538484B2 (en) * 2006-10-24 2010-09-08 太陽インキ製造株式会社 Photocurable thermosetting resin composition and printed wiring board using the same
JP5066376B2 (en) * 2007-02-27 2012-11-07 株式会社タムラ製作所 Solder resist composition for printed wiring board and printed wiring board
JP4601009B2 (en) * 2007-03-30 2010-12-22 富士フイルム株式会社 Ink set for inkjet recording and inkjet recording method
JP2009194222A (en) * 2008-02-15 2009-08-27 Denki Kagaku Kogyo Kk White alkali-developable photocurable and thermosetting solder resist composition, and metal-base circuit substrate using the same
JP2010014767A (en) * 2008-07-01 2010-01-21 Denki Kagaku Kogyo Kk Alkali developable photocurable/heat curable solder resist composition and metal base circuit board using the same
JP5485599B2 (en) * 2008-08-26 2014-05-07 株式会社タムラ製作所 Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board

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