CN108329755A - Ink-jet solidification compound, solidfied material and printed circuit board - Google Patents
Ink-jet solidification compound, solidfied material and printed circuit board Download PDFInfo
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- CN108329755A CN108329755A CN201810049580.1A CN201810049580A CN108329755A CN 108329755 A CN108329755 A CN 108329755A CN 201810049580 A CN201810049580 A CN 201810049580A CN 108329755 A CN108329755 A CN 108329755A
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- ink
- jet
- solidification compound
- viscosity
- optical polymerism
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Classifications
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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
-
- 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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- 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
-
- 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
Abstract
The present invention relates to ink-jet solidification compound, solidfied material and printed circuit boards.It provides：Solder mask, the film of sign flag are formed with ink jet printing method and surface cure when being cured is good and the good ink-jet solidification compound of adaptation.The present invention ink-jet include with solidification compound：(A) the optical polymerism monofunctional monomer with cyclic skeleton；(B) viscosity at 25 DEG C is 100mPas 2 functional monomers of optical polymerism below；(C) viscosity at 25 DEG C is the optical polymerism polyfunctional monomer of 500mPas or less and 3 functions or more；With (D) Photoepolymerizationinitiater initiater.
Description
Technical field
The present invention relates to：It is suitable for forming the solder mask of such as printed circuit board, sign flag by ink jet printing method
Ink-jet solidification compound, solidfied material and printed circuit board using it.
Background technology
Ink jet printing method is following method：Using ink-jet printer, after the drop of Photocurable composition is discharged to base material,
Irradiation UV isoreactivity energy-rays make it cure immediately.Ink jet printing method can directly be painted defined printed patterns by numerical data
System, therefore can cut down the dosage of ink, compared with the conventional method, can be effectively performed life without the version of silk-screen printing
Production.In addition, ink jet printing method is off-contact printing, therefore, be easy printing to irregular base material, there is base material flexible,
Expect to be used for printed wiring material.
For example, in printed wiring material, the solder mask formed as outermost protective film is printed by application ink-jet
Brush method is easy to carry out the management of production line without the exposure imaging technique in the silk screen print method of previous alkali developable,
It forms a film in environment amenable method.
The ink of ink jet printing is compared with the ink of previous silk-screen printing, it is necessary to be low viscosity so that can be beaten with ink-jet
Print machine is discharged, such as viscosity when coating is necessary for 50mPs or less.Therefore the ink-jet for the viscosity for having adjusted monomer component uses
Anti-corrosion agent composition (patent document 1).
Existing technical literature
Patent document
Patent document 1：Japanese Patent No. 4456833
Invention content
Problems to be solved by the invention
Previous ink-jet is adapted for the ink of low viscosity with solidification compound, and therefore, dissolving, the diffusion of oxygen are fast.In addition, spray
Ink is discharged in ink print method in the form of small drop, therefore, the large specific surface area of drop when discharge, it is easier to dissolved oxygen.
For those reasons, when UV solidifications after ink jet printing, ink is easy by being hindered cured, so-called oxygen due to the oxygen in air
It hinders, the surface cure of cured coating film is easily reduced as a result,.For lowering viscousity, and include largely low in addition, for ink
Therefore the diluent of viscosity is easily reduced with various characteristics such as the adaptations of substrate.Solder mask, the symbol mark of printed circuit board
The substrate adaptation of note is especially important, hence it is desirable to use ink jet printing method is by the high solder mask of substrate adaptation, symbol
Label forms a film.
The present invention makes to effectively solve the above problems, it is intended that providing：Utilize ink jet printing method shape
At film, cured when surface cure is good and the good ink-jet solidification compound of adaptation, consolidating using it
Compound and printed circuit board.
The solution to the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that：Combination has particular kind of light
Light more than polymerism monofunctional monomer, particular viscosity 2 functional monomer of optical polymerism below and particular viscosity 3 function below
The composition of polymerism polyfunctional monomer can obtain good surface cure and adaptation, result in the spray of the present invention
Ink solidification compound.
The present invention ink-jet solidification compound be characterized in that, including：(A) the optical polymerism list with cyclic skeleton
Functional monomer；(B) viscosity at 25 DEG C is 100mPas 2 functional monomers of optical polymerism below；(C) viscosity at 25 DEG C is
Optical polymerism polyfunctional monomers more than 500mPas or less and 3 functions；With (D) Photoepolymerizationinitiater initiater.
The ink-jet of aforementioned present invention is preferably with solidification compound, has the light of cyclic skeleton poly- as above-mentioned (A)
Conjunction property monofunctional monomer, including：Monofunctional monomer with cyclic annular hydrocarbon skeleton and the monofunctional monomer with heterocyclic skeleton, more
Preferably comprise the monofunctional monomer of more than two kinds that there should be heterocyclic skeleton.
In addition, the ink-jet of aforementioned present invention is preferably with solidification compound, also include the compound with triazine ring.
The solidfied material of the present invention is the solidfied material of above-mentioned ink-jet solidification compound.
The printed circuit board of the present invention has above-mentioned solidfied material.
The effect of invention
The ink jet printing of the ink-jet solidification compound of the present invention is excellent and can take into account based on ink jet printing method
The good surface cure of film and good adaptation.In addition, by the present invention ink-jet curing composition into
Row light irradiates, and on the basis of surface cure and adaptation, can also obtain each excellents such as pencil hardness, resistance to plating
Solidfied material.In turn, ink-jet curing composition of the invention can be formed on the base material of printed circuit board and pass through light
Irradiation forms above-mentioned solidfied material to have.
Specific implementation mode
The present invention ink-jet solidification compound be characterized in that, including：(A) the optical polymerism list with cyclic skeleton
Functional monomer；(B) viscosity at 25 DEG C is 100mPas 2 functional monomers of optical polymerism below；(C) viscosity at 25 DEG C is
Optical polymerism polyfunctional monomers more than 500mPas or less and 3 functions；With (D) Photoepolymerizationinitiater initiater.
It should be noted that in present specification, ink-jet refers to solidification compound, for making solidification compound
It is expelled on base material and the composition of the method for printing word, pattern in a non contact fashion, for example, further including：For not only leading to
Cross the print processes such as piezo electrics, hot mode, electrostatic means also by using print process of injector etc. by word, pattern print to
Composition on base material.
[(A) has the optical polymerism monofunctional monomer of cyclic skeleton]
The ink-jet of present invention solidification compound includes the optical polymerism monofunctional monomer with cyclic skeleton.With ring
The optical polymerism monofunctional monomer of shape skeleton reduces the viscosity of the ink-jet solidification compound of the present invention as diluent.Separately
Outside, the adaptation of the solidfied material of the ink-jet solidification compound of the present invention is maintained, and raising hardness of film, particularly pencil are hard
Degree.Optical polymerism monofunctional monomer with cyclic skeleton and the optical polymerism monofunctional monomer, such as without cyclic skeleton
Butyl acrylate etc. is compared, and adaptation and surface cure can be made to improve.Therefore, by poly- comprising the light with cyclic skeleton
Conjunction property monofunctional monomer can be obtained than previous excellent adaptation and surface cure.
As the optical polymerism monofunctional monomer with cyclic skeleton, (methyl) isobornyl acrylate, (first can be enumerated
Base) tetrahydrofurfuryl acrylate, (methyl) glycidyl acrylate, gamma-butyrolacton (methyl) acrylate, gamma-butyrolacton (first
Base) (methyl) the acryloyl base class such as (methyl) esters of acrylic acid, the acryloyl morpholine such as acrylate.It should be noted that this
In specification, (methyl) acrylate refers to being referred to as the term of acrylate and methacrylate, and (methyl) acryloyl group is
Refer to, is referred to as the term of acryloyl group and methylacryloyl.
(A) the optical polymerism monofunctional monomer with cyclic skeleton is preferably by (methyl) isobornyl acrylate etc. with ring
The monofunctional monomer of shape hydrocarbon skeleton and (methyl) tetrahydrofurfuryl acrylate, (methyl) glycidyl acrylate, gamma-butyrolacton
There is the monofunctional monomer of heterocyclic skeleton to be applied in combination for (methyl) acrylate, (methyl) acryloyl morpholine etc..By comprising
Monofunctional monomer with cyclic annular hydrocarbon skeleton can obtain excellent adaptation.Monofunctional monomer with heterocyclic skeleton and tool
There is the monofunctional monomer of cyclic annular hydrocarbon skeleton to compare, oxygen obstruction is not easily susceptible to, therefore, by including single official with heterocyclic skeleton
Energy monomer, can obtain excellent surface cure.Therefore, by will have the monofunctional monomer of cyclic annular hydrocarbon skeleton, with have
The monofunctional monomer of heterocyclic skeleton is applied in combination, and excellent adaptation and excellent surface cure can be taken into account with higher level
Property.
Under the above situation, the monofunctional monomer with heterocyclic skeleton combines two or more in use, can be according to each simple function
The characteristic of monomer takes into account excellent adaptation and excellent surface cure with further high level, therefore it is preferred that.
(A) curing composition 100 of the compounding amount of the optical polymerism monofunctional monomer with cyclic skeleton in the present invention
Preferably 10~80 mass parts in mass parts.By contained above with 10 mass parts, adaptation, surface cure become good.In addition,
By with 80 it is below mass part include that can prevent the reduction of the crosslink density in solidfied material, coating characteristic becomes good.
In addition, comprising with cyclic annular hydrocarbon skeleton monofunctional monomer and the case where with the monofunctional monomer of heterocyclic skeleton
Under, relative to 100 mass parts of monofunctional monomer with cyclic annular hydrocarbon skeleton, the mix ratio of the monofunctional monomer with heterocyclic skeleton
Example preferably 12.5~600 mass parts.
The solidification compound of the present invention is used for ink-jet method, it is therefore preferable that abundant low viscosity, such as be at 50 DEG C
50mPas or less.It should be noted that in present specification, viscosity is the value measured according to JIS K2283.
[viscosity at 25 DEG C of (B) is 100mPas 2 functional monomers of optical polymerism below]
The ink-jet of the present invention is 100mPas optical polymerisms 2 below comprising the viscosity at 25 DEG C with solidification compound
Functional monomer.For 2 functional monomer of optical polymerism compared with polyfunctional monomer more than aftermentioned 3 function, reactivity is low, therefore, passes through
It is applied in combination with monofunctional monomer, as the diluent of polyfunctional monomers more than 3 functions, makes the ink-jet curability of the present invention
The viscosity of composition reduces, and therefore reactivity makes surface cure improve higher than monofunctional monomer.However, if light is poly-
The viscosity of 2 functional monomers of conjunction property is high, then the viscosity of ink-jet solidification compound is got higher.By making 2 functional monomer of optical polymerism
25 DEG C at viscosity be 100mPas hereinafter, 2 functions (methyl) acrylate compounds as diluent operability change it is good
It is good, each ingredient can be made uniformly to mix.As a result, can expect that the whole face of film is similarly closely sealed to base material.2 official of optical polymerism
Viscosity preferably 1~100mPas, particularly preferred 3~30mPas at 25 DEG C of energy monomer.
It is 100mPas 2 functional monomers of optical polymerism below as the viscosity at 25 DEG C, for example, 2- hydroxyls
Base -3- acryloxypropyls (methyl) acrylate, two (methyl) acrylate of hydroxyl neopentyl hydroxyl peopentyl ester, 1,3- fourths
Glycol two (methyl) acrylate, 2- methyl-1s, 3- butanediols two (methyl) acrylate, 1,4- butanediols two (methyl) propylene
Acid esters, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, two (first of 1,10- decanediols
Base) acrylate, 3- methyl-1s, 5- pentanediols two (methyl) acrylate, ethoxylation 1,6-HD two (methyl) propylene
Acid esters, neopentyl glycol two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, polyethylene glycol #200 bis-
(methyl) acrylate, polyethylene glycol #400 bis- (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol
Two (methyl) acrylate, polypropylene glycol #400 bis- (methyl) acrylate, polypropylene glycol (#700) two (methyl) acrylate,
1,10- decanediols two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediols two (methyl) propylene
Acid esters, neopentyl glycol two (methyl) acrylate, glycerine two (methyl) acrylate, ethylene glycol two (methyl) acrylate, two
Ethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyethylene glycol #200 bis- (methyl) acrylate,
Polyethylene glycol #400 bis- (methyl) acrylate, polyethylene glycol #600 bis- (methyl) acrylate, bis- (first of polyethylene glycol #1000
Base) acrylate, ethoxylated polypropylene glycol #700 bis- (methyl) acrylate, polypropylene glycol #400 bis- (methyl) acrylate
Deng.It can use one kind or two or more in them.
(B) viscosity at 25 DEG C is compounding amount the consolidating in the present invention of 100mPas 2 functional monomers of optical polymerism below
Preferably 10~80 mass parts in 100 mass parts of change type composition.By contained above with 10 mass parts, curability can be made to combine
Object be abundant low viscosity, such as at 50 DEG C be 50mPas or less.By with 80 it is below mass part include adaptation, surface
Curability becomes good.
[viscosity at 25 DEG C of (C) is the optical polymerism polyfunctional monomer of 500mPas or less and 3 functions or more]
The present invention ink-jet with solidification compound include 25 DEG C at viscosity be 500mPas or less and 3 functions more than
Optical polymerism polyfunctional monomer.The reactivity of optical polymerism polyfunctional monomers more than 3 functions is high, and surface cure is made to carry
It is high.However, if the viscosity of optical polymerism polyfunctional monomers more than 3 functions is high, the viscosity of ink-jet solidification compound
It gets higher.The viscosity at 25 DEG C of optical polymerism polyfunctional monomer by making 3 functions or more be 500mPas hereinafter, to
The optical polymerism monofunctional monomer of other compositions, 2 functional monomer of optical polymerism match, and can be easily discharged from ink gun.3
Viscosity at 25 DEG C of more than function optical polymerism polyfunctional monomer be, for example, 10~500mPas, preferably 30~
100mPa·s。
It is the optical polymerism polyfunctional monomer of 500mPas 3 functions below or more for the viscosity at 25 DEG C, such as makees
For 3 function optical polymerism polyfunctional monomers, can enumerate：
Ethoxylated trimethylolpropane triacrylate (TMP3EOTA, TMP9EOTA),
Propoxylation trimethylolpropane trimethacrylate (TMP3POTA),
Trimethylolpropane trimethacrylates and the epoxies such as propoxylated glycerol triacrylate (G3POTA, G3.5POTA)
Alkane modifier；
The trimethylolpropanes such as ethoxylated trimethylolpropane trimethyl acrylic ester (TMP3EOTMA, TMP9EOTMA)
Trimethyl acrylic ester and alkylene oxide modifier；
Pentaerythrite three (methyl) acrylate；
As 4 function optical polymerism polyfunctional monomers, pentaerythrite four (methyl) acrylate, ethoxylation can be enumerated
Pentaerythrite four (methyl) acrylate (EO35mol)
Deng, can use they in it is one kind or two or more.
(C) viscosity at 25 DEG C is the compounding amount of the optical polymerism polyfunctional monomer of 500mPas or less and 3 functions or more
Preferably 20~50 mass parts in 100 mass parts of curing composition of the present invention.By contained above with 20 mass parts, solidification
Property composition surface cure fully become high rigidity, by with 50 it is below mass part include that viscosity becomes good.
[(D) Photoepolymerizationinitiater initiater]
The ink-jet of present invention solidification compound includes Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be enumerated
The benzoins such as acyloin isopropyl ether and benzoin alkyl ethers；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- bis-
The acetophenones such as ethyoxyl -2- phenyl acetophenones, 1,1- dichloroacetophenones；2- methyl-1s-[4- (methyl thio) phenyl] -2-
Quinoline base propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butane -1- ketone, 2- (dimethylamino) -
2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- butanone, N, the aminobenzenes such as N- dimethylamino benzoylformaldoximes
Ethyl ketone class；The Anthraquinones such as 2-methylanthraquinone, 2- ethyl hydrazine, 2- tertiary butyls anthraquinone, 1- chloroanthraquinones；2,4- dimethyl thioxanthones,
The thioxanthene ketone class such as 2,4- diethyl thioxanthones, 2-chlorothioxanthone, 2,4- diisopropylthioxanthones；Acetophenone dimethyl ketal, benzene
The ketals classes such as even acyl dimethyl ketal；2,4,5- triarylimidazoles dimers；Hibon；2-mercaptobenzimidazole, 2-
The mercaptan compounds such as mercaptobenzoxazole, 2-mercaptobenzothiazole；Tri--s-triazine of 2,4,6-, 2,2,2- ethobroms, tribromo first
The organohalogen compounds such as base phenylsulfone；Benzophenones or the xanthenes such as benzophenone, 4,4 '-bis- diethylamino benzophenone
Class；The phosphinoxides such as 2,4,6- trimethyl benzoyl diphenyl base phosphine oxides.
Photoepolymerizationinitiater initiater can use it a kind of, can also combine two or more use.
(D) model of the compounding ratio of Photoepolymerizationinitiater initiater preferably 1~15 mass parts in 100 mass parts of solidification compound
It encloses.
The ink-jet solidification compound of the present invention can include the compound with triazine ring.Chemical combination with triazine ring
Object can enumerate known common substance, specifically, guanamines, acetylguanamine, benzoguanamine, melamine etc. can be enumerated.
Compound with triazine ring can be used alone or be used in the form of mixture of more than two kinds.There is triazine by compounding
The compound of ring can assign the film of solidification compound hardness, and pencil hardness becomes good, and can obtain and adaptation
Harmony.
Wherein, from the viewpoint of improving pencil hardness, any one of amino and unsaturated double-bond or more are preferably provided with
The compound with triazine ring can enumerate guanamines, acetyl guanidine as the concrete example of such compound with triazine ring
Amine, benzoguanamine, melamine, 2,4- diamino -6- vinyl-s-triazine (Shikoku Chem VT), 2,
4- diamino -6- methyacryloxyethyls-s-triazine (Shikoku Chem MAVT), 2,4- diamino -
6- vinyl-s-triazine isocyanuric acid adduct (Shikoku Chem VT-OK) etc..Especially by including three
Poly cyanamid, adaptation further increase.
The compounding ratio of compound with triazine ring preferably 1~10 mass parts in 100 mass parts of solidification compound
Range.
[colorant]
The present invention ink-jet solidification compound can include：Phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow,
The colorants such as common pigment, dyestuff known in crystal violet, titanium oxide, carbon black, naphthalene are black etc..
Such colorant can be used alone or mix two or more use, and compounding amount is relative to ink-jet curability
100 mass parts of nonvolatile component of composition are 0.1~30 parts by weight, preferably 0.5~2 mass parts.The compounding amount of colorant is
When more than 0.1 mass parts, visuality improves, and when being 30 below mass part, the photo-curable of film lower part improves.
Including when white pigment is as colorant, can use titanium oxide, zinc oxide, magnesia, zirconium oxide, aluminium oxide,
Well known to barium sulfate, silica, talcum, mica, aluminium hydroxide, calcium silicates, alumina silicate, hollow resin particles, zinc sulphide etc.
White pigment.Wherein, from high coloring and reflectivity aspect, preferably titanium oxide.These white pigments can be independent
It is used singly, or in combination of two or more kinds.Titanium oxide can be that Titanium Dioxide Rutile Top grade may be Detitanium-ore-type oxidation
Titanium, from coloring, concealment and stability aspect, it is preferable to use Titanium Dioxide Rutile Top grade.As identical titanium oxide
For anatase-type titanium oxide compared with Titanium Dioxide Rutile Top grade, whiteness is high, through being used frequently as white pigment, but Detitanium-ore-type oxygen
Changing titanium, there is photocatalytic activity therefore especially because from the light of LED illumination, to cause in insulating resin composition sometimes
The discoloration of resin.In contrast, the whiteness of Titanium Dioxide Rutile Top grade is slightly worse compared with Detitanium-ore-type, but does not have light substantially and live
Property, therefore, the deterioration (xanthochromia) for being originated from the resin caused by the photoactive light of titanium oxide is suppressed significantly, and for heat
It is stable.Therefore, it is equipped in the insulating layer of the printed circuit board of LED, in use, it can be after long-term as white pigment
Ground maintains high reflectance.
As Titanium Dioxide Rutile Top grade, well known substance can be used.The autofrettage of Titanium Dioxide Rutile Top grade includes sulfuric acid
This 2 kinds of method and chlorine method in of the invention, can compatibly use the substance manufactured by arbitrary autofrettage.Herein, sulfuric acid process refers to
Following preparation method：Using ilmenite ore, Titanium slag as raw material, it is dissolved in the concentrated sulfuric acid, ferrous components are divided in the form of ferric sulfate
From, solution is hydrolyzed, to obtain the sediment of hydroxide, it is roasted at high temperature, taking-up Titanium Dioxide Rutile Top grade.Separately
On the one hand, chlorine method refers to following preparation method：Using titania, natural rutile as raw material, make it at a high temperature of about 1000 DEG C
It is reacted with chlorine and carbon to synthesize titanium tetrachloride, is oxidized taking-up Titanium Dioxide Rutile Top grade.Wherein, for being manufactured by chlorine method
Titanium Dioxide Rutile Top grade, it is especially hot caused by resin deterioration (xanthochromia) inhibition it is notable, it is more suitable in the present invention
It closes and uses.
Influence of the compounding amount of white color agents to absorbance is big, preferably 5~50 in 100 mass parts of solidification compound
Mass parts, more preferable 10~30 mass parts, particularly preferred 20~30 mass parts.White pigment if it is 5 mass parts more than, group
The reflectivity for closing object becomes abundant.It is below mass part if it is 50, it can be with the rising and printing of the viscosity surplus of composite inhibiting
The reduction of property.
Including when black colorant is as colorant, carbon, nigrosine, iron oxide etc. can be used.The compounding of black pigment
The influence measured to absorbance is big, preferably 5~50 mass parts, more preferable 10~30 mass in 100 mass parts of solidification compound
Part, particularly preferred 20~30 mass parts.
Can include Ricinate in the ink-jet solidification compound of the present invention.As Ricinate, can make
With the general substance having the effect of for auxiliary pigment dispersion.As such Ricinate, can use：With carboxylic
Base, hydroxyl, the compound of acid esters isopolarity group, high-molecular compound, such as phosphoric acid ester etc. containing acid compound, comprising acid
The salt etc. of the copolymer of base, the polycarboxylate of hydroxyl, polysiloxanes, long-chain polyaminoamide and acid esters.
In addition, in these Ricinates, the substance with acid value, the dispersion by inorganic pigments such as titanium oxide is that have
Effect, therefore it is preferred that.
As the concrete example of the Ricinate with acid value, Anti-Terra-U, Anti-Terra- can be enumerated
U100、Anti-Terra-204、Anti-Terra-205、Disperbyk-101、Disperbyk-102、Disperbyk-106、
Disperbyk-110、Disperbyk-111、Disperbyk-130、Disperbyk-140、Disperbyk-142、
Disperbyk-145、Disperbyk-170、Disperbyk-171、Disperbyk-174、Disperbyk-180、
Disperbyk-2001、Disperbyk-2025、Disperbyk-2070、Disperbyk-2096、BYK-P104、BYK-
P104S, BYK-P105, BYK-9076, BYK-220S (being BYK Chemie Co. Ltd. systems) etc..
The acid value of these Ricinates with acid value preferably 10~300mgKOH/g.
The compounding amount of above-mentioned Ricinate is relative to 100 mass parts of colorant preferably 5~75 mass parts.
Can include surface tension modifier in the ink-jet solidification compound of the present invention.Surface tension modifier is matched
Mixed amount is relative to 100 mass parts of composition preferably 0.01~5 mass parts.
In the ink-jet solidification compound of the present invention, in addition to the above ingredients, it can be compounded surface-active as needed
Agent, delustering agent, the polyester based resin for adjusting film physical property, polyurethane series resin, vinyl resin, acrylic resin,
At least one kind of, imidazoles system, thiazole in the antifoaming agent and levelling agent such as rubber series resin, wax class, silicone-based, fluorine system, macromolecular
Known common additive kind as the adaptations imparting agents such as system, triazole system, silane coupling agent.
For the solidification compound with above-mentioned each ingredient, from for ink-jet method aspect, solidification compound
50 DEG C at viscosity preferably 5~50mPas, more preferable 5~20mPas.Will not be caused as a result, to ink-jet printer need not
The load wanted can be smoothed out printing.
The viscosity of solidification compound refers to the viscosity measured at room temperature (25 DEG C) or 50 DEG C according to JIS K2283.Such as
Be viscosity at 150mPas or less or 50 DEG C under fruit room temperature it is 5~50mPas, then can be carried out using ink jet printing method
Good printing.
In addition, preferably 0.1~5 μm or less of the maximum particle diameter of particle contained in solidification compound, more preferable 0.1~1 μ
m.Maximum particle diameter is if it is 0.1 μm or more, and the aggregation force of particle will not become excessively high, if it is 5 μm hereinafter, ink-jet then occurs
The possibility of the problems such as spray nozzle clogging when printing is lower, therefore it is preferred that.The maximum particle diameter of particle contained in composition can profit
It is measured with particle size distribution meter, using its D100 value as maximum particle diameter.
＜ solidfied materials ＞
After the solidification compound of the present invention is coated on base material in the way of ink-jet, illumination is carried out with light source using light irradiation
It penetrates, so as to form solidfied material.
Light irradiation is carried out by irradiating ultraviolet light or active energy beam, preferably ultraviolet light.As light irradiation light source,
It is appropriate that low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, metal halide lamp, LED (light-emitting diodes
Pipe) UV lamp etc..As the wavelength of light source, 365nm, 385nm, 395nm, 405nm etc. can be enumerated, by using the light of short wavelength
Source can expect more good surface cure.
In addition it is also possible to utilize electron beam, alpha ray, β rays, gamma-rays, X-ray, neutron beam etc..
And then cured as needed by heating after light irradiation.Herein, heating temperature is, for example, 80~200 DEG C.
By being set as above-mentioned heating temperature range, solidification can be sufficiently carried out.Heating time is, for example, 10~100 minutes.
＜ printed circuit boards ＞
Printed circuit board has the solidfied material of ink-jet solidification compound, specifically, in the base with circuit pattern
There is the solidfied material formed by solidification compound on material.Printed circuit board can manufacture by the following method.
First, solidification compound is adjusted to the viscosity suitable for coating method with organic solvent as needed, with ink-jet
Mode is coated on the base material for being formed with circuit, is formed and has figuratum solidfied material.Herein, solidification compound includes that light produces alkali
When agent, be preferably heating and curing after being irradiated for cured light object.Heating temperature is, for example, 80~200 DEG C.
The solidification compound of the present invention is used as the ink of ink-jet mode in application, can be to flexible electrical by above-mentioned composition
Road plate carries out the printing of roll-to-roll mode.In addition, the solidification compound of the present invention such as comprising to be polyimides
The printed circuit board of the plastic basis material of principal component and the conductor circuit being arranged on, can form surface cure and adaptation
Each excellents such as the gold-plated property of excellent and resistance to soldering heat performance, chemical resistance, solvent resistance, pencil hardness, chemically-resistant
Pattern cured coating film.
Solidification compound is suitable as the solidfied material formation material of printed circuit board, is especially suitable as printing electricity
The permanent overlay film formation material of road plate, wherein be suitable as solder mask, the sign flag that is formed on solder mask etc. it is permanent absolutely
Velum formation material.
Embodiment
Hereinafter, show that the present invention is specifically described in embodiment, but the present invention is not limited to these embodiments.It needs
Illustrate, below in unless otherwise specified, " part " refers to mass parts.
Prepare polyfunctional monomer, the Photoepolymerizationinitiater initiater of monofunctional monomer, 2 functional monomers, 3 functions shown in table 1 or more
And additive.
[table 1]
Suitable for using each ingredient in table 1 to be pre-mixed with blender, ink-jet solidification compound is prepared.It will implement
Example 1~8, each ingredient of comparative example 1~6 and compounding amount are shown in table 2.
[table 2]
Using the ink-jet solidification compound of Examples 1 to 8, comparative example 1~6 shown in table 2, under the following conditions
It is drawn using ink-jet printer on base material, then cures its UV, test substrate is made.It should be noted that as base material,
It uses use in printed circuit board copper-clad laminated board (FR-4,150mm × 95mm × 1.6mm).
＜ utilizes the drafting condition ＞ of ink-jet printer
Film thickness：20μm
Device：Using piezo electrics ink-jet printer (FUJIFILM Global Graphic Systems Co.,
Ltd. Materials Printer DMP-2831 (head temperature 50 C) processed)
＜ UV conditions of cure ＞
Light exposure：1000mJ/cm2
Wavelength：385nm
The UV curability of ink-jet injection property and film when investigation ink jet printing, adaptation, hardness of film, chemically-resistant plating
Ni-Au.Each evaluation criteria is as described below.
(1) ink jet printing (injection property)
Drop can be made continuous as the crow flies and steadily projected：〇
It can not carry out the injection of droplets stable：×
It should be noted that project it is unstable and when can not be coated with, it is unreal impose after evaluation.
(2) surface cure (UV curability)
The surface of solidfied material, evaluation adhesion (viscosity) are contacted with finger.
Without adhesion：◎
There is adhesion, but non-transfer：○
There is adhesion, it is seen that a little transfer：△
Liquid-like constituents remain：×
(3) adaptation
For cured coating film, implementation basis JIS K 5400:1990 stroke lattice belt stripping test, is evaluated.
Without stripping：〇
There is a little stripping：△
There is stripping：×
(4) pencil hardness (hardness of film)
It is measured according to JIS K 5400.
(5) chemically-resistant plates Ni-Au
It is bathed using commercially available Electroless Plating Ni/Au, in Ni：0.5μm、Au：Chemical nickel plating gold is carried out under conditions of 0.3 μm, into
The observation of the surface state of row cured coating film judges albefaction with following evaluation criteria.
No albefaction expansion：〇
There is a little surface albefaction：△
There are surface albefaction and expansion：×
In addition, to the adaptation implementation basis JIS K 5400 of the cured coating film after Electroless Plating Ni/Au:1990 stroke lattice glue
Band disbonded test evaluates adaptation with following evaluation criteria.
Without stripping：〇
There is a little stripping：△
There is stripping：×
Examples 1 to 8, the evaluation result of comparative example 1~6 are recorded in table 2 together.
As shown in Table 2, ink jet printing, surface cure, close for the Examples 1 to 8 for the composition for using the present invention
Conjunction property, pencil hardness, chemically-resistant plating Ni-Au are excellent.Wherein, for comprising with cyclic annular hydrocarbon skeleton monofunctional monomer and
Monofunctional monomer with heterocyclic skeleton and the embodiment 2~3 for being somebody's turn to do the monofunctional monomer with heterocyclic skeleton containing 2 kinds, pencil
Hardness is high, can obtain excellent surface cure.Especially for the embodiment 3 comprising melamine, pencil hardness higher,
It can obtain excellent surface cure.
In contrast, for comprising butyl acrylate and without the comparative example 1 of the monofunctional monomer with cyclic annular hydrocarbon skeleton,
Surface cure, resistance to plating equal difference.
In addition, for the comparative example 2 without the viscosity at 25 DEG C for 100mPas 2 functional monomers of optical polymerism below,
The compounding amount of 3 functional monomers is more, can not carry out ink jet printing.
In addition, for the comparative example 3 without the viscosity at 25 DEG C for 100mPas 2 functional monomers of optical polymerism below,
The compounding amount of monofunctional monomer is more, surface cure, pencil hardness equal difference.
In addition, for replaced by 100mPas 2 functional monomers of optical polymerism below without the viscosity at 25 DEG C comprising
Viscosity at 25 DEG C is more than the comparison of 2 functional monomers of optical polymerism, that is, Tricyclodecane Dimethanol diacrylate of 100mPas
Example 4 can not carry out ink jet printing.
In addition, for without the multifunctional list of optical polymerism that the viscosity at 25 DEG C is 500mPas 3 functions below or more
The comparative example 5 of body, the compounding amount of monofunctional monomer is more, and compared with comparative example 3, surface cure, resistance to plating are also poor.
In addition, for without the multifunctional official of optical polymerism that the viscosity at 25 DEG C is 500mPas 3 functions below or more
Can monomer and replace being more than optical polymerism polyfunctional monomer i.e. three more than 3 functions of 500mPas comprising the viscosity at 25 DEG C
The comparative example 6 of (2- hydroxyethyls) isocyanurate triacrylate, can not carry out ink jet printing.
(embodiment 9~11)
For embodiment 9~11, as shown in Table 3, so that each composition is cured with different light sources and is made test substrate,
In addition to this, similarly to Example 8.
As shown in Table 3, for use the present invention composition embodiment 9~11, ink jet printing, surface cure,
Adaptation, pencil hardness, chemically-resistant plating Ni-Au are excellent.In particular, the light emitting diode (LED) for using wavelength 365nm
As the embodiment 9 of light source, surface cure is good.
[table 3]
Claims (5)
1. a kind of ink-jet solidification compound, which is characterized in that include：
(A) the optical polymerism monofunctional monomer with cyclic skeleton；
(B) viscosity at 25 DEG C is 100mPas 2 functional monomers of optical polymerism below；
(C) viscosity at 25 DEG C is the optical polymerism polyfunctional monomer of 500mPas or less and 3 functions or more；
(D) Photoepolymerizationinitiater initiater；With,
Compound with triazine ring, the compound with triazine ring have except (D) Photoepolymerizationinitiater initiater as described in
Except the compound of triazine ring.
2. ink-jet solidification compound according to claim 1, wherein have the light of cyclic skeleton as (A)
Polymerism monofunctional monomer, including：Monofunctional monomer with cyclic annular hydrocarbon skeleton and the monofunctional monomer with heterocyclic skeleton.
3. ink-jet solidification compound according to claim 2 is comprising of more than two kinds described with heterocycle bone
The monofunctional monomer of frame.
4. a kind of solidfied material of ink-jet solidification compound according to any one of claims 1 to 3.
5. a kind of printed circuit board, the solidfied material with the ink-jet curing composition described in claim 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-008672 | 2017-01-20 | ||
| JP2017008672A JP6209690B1 (en) | 2017-01-20 | 2017-01-20 | Curable composition for inkjet, cured product, and printed wiring board |
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| CN108329755A true CN108329755A (en) | 2018-07-27 |
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| CN201810049580.1A Pending CN108329755A (en) | 2017-01-20 | 2018-01-18 | Ink-jet solidification compound, solidfied material and printed circuit board |
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| JP (1) | JP6209690B1 (en) |
| KR (1) | KR20180086144A (en) |
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| CN113993295A (en) * | 2021-10-13 | 2022-01-28 | 苏州康尼格电子科技股份有限公司 | PCBA board encapsulation UV glue solution and shower nozzle suitable for piezoelectric array shower nozzle |
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| CN107858044B (en) * | 2017-10-09 | 2020-11-13 | 广东高仕电研科技有限公司 | UV (ultraviolet) curing jet printing ink and preparation method thereof |
| WO2020179155A1 (en) * | 2019-03-06 | 2020-09-10 | 富士フイルム株式会社 | Ink-jet ink composition, method for recording image, and object with recorded image |
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| CN101432374A (en) * | 2006-04-28 | 2009-05-13 | Jsr株式会社 | Energy ray-curable inkjet printing ink |
| CN104516204A (en) * | 2013-09-30 | 2015-04-15 | 太阳油墨制造株式会社 | Curable composition for printed circuit board, cured coating film using the same, and printed circuit board |
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| JP4456833B2 (en) | 2003-07-24 | 2010-04-28 | 太陽インキ製造株式会社 | One-component resist composition for inkjet and method for forming resist pattern using the same |
| JP4852953B2 (en) * | 2004-09-30 | 2012-01-11 | セイコーエプソン株式会社 | Ink composition and image forming method using the same |
| JP5650016B2 (en) * | 2011-02-28 | 2015-01-07 | 富士フイルム株式会社 | Inkjet recording method and printed matter |
| JP5703981B2 (en) * | 2011-06-07 | 2015-04-22 | セイコーエプソン株式会社 | Photocurable ink composition for ink jet recording and ink jet recording method |
| JP6171474B2 (en) * | 2013-03-28 | 2017-08-02 | Dic株式会社 | Active energy ray-curable ink composition for inkjet recording and image forming method |
| JP5800968B1 (en) * | 2014-08-08 | 2015-10-28 | 株式会社Ｄｎｐファインケミカル | Active energy ray-curable ink composition, laminate using the ink composition, and image forming method for forming an image on a substrate |
| JP6825207B2 (en) * | 2015-03-13 | 2021-02-03 | 株式会社リコー | Active energy ray-curable composition, active energy ray-curable ink, containment vessel, two-dimensional or three-dimensional image forming device, two-dimensional or three-dimensional image forming method, two-dimensional or three-dimensional image, structure, and Molded product |
| JP6915230B2 (en) * | 2015-06-16 | 2021-08-04 | 株式会社リコー | An active energy ray-curable composition, an active energy ray-curable ink, a composition container, a method and an apparatus for forming a two-dimensional or three-dimensional image, a molded product, and a dispersibility evaluation apparatus. |
| JP6168180B2 (en) * | 2016-03-02 | 2017-07-26 | セイコーエプソン株式会社 | Photocurable ink composition and recording method |
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- 2018-01-18 KR KR1020180006533A patent/KR20180086144A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101432374A (en) * | 2006-04-28 | 2009-05-13 | Jsr株式会社 | Energy ray-curable inkjet printing ink |
| CN104516204A (en) * | 2013-09-30 | 2015-04-15 | 太阳油墨制造株式会社 | Curable composition for printed circuit board, cured coating film using the same, and printed circuit board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113993295A (en) * | 2021-10-13 | 2022-01-28 | 苏州康尼格电子科技股份有限公司 | PCBA board encapsulation UV glue solution and shower nozzle suitable for piezoelectric array shower nozzle |
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| JP6209690B1 (en) | 2017-10-04 |
| JP2018115297A (en) | 2018-07-26 |
| KR20180086144A (en) | 2018-07-30 |
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