CN101189550A - Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same - Google Patents
Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same Download PDFInfo
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- CN101189550A CN101189550A CNA2006800192950A CN200680019295A CN101189550A CN 101189550 A CN101189550 A CN 101189550A CN A2006800192950 A CNA2006800192950 A CN A2006800192950A CN 200680019295 A CN200680019295 A CN 200680019295A CN 101189550 A CN101189550 A CN 101189550A
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Abstract
A photocurable and thermosetting resin composition comprising (A) a carboxyl-group containing resin, (B) an oxime ester-based photopolymerization initiator containing an oxime ester group, (C) an aminoacetophenone-based photopolymerization initiator and/or a phosphine oxide-based photopolymerization initiator, (D) a compound having at least two ethylenically unsaturated groups in its molecule, (E) a filler, and (F) a thermosetting component is capable of being developed with a dilute alkaline solution and cured with a laser emission source having a maximum wavelength of 350 nm to 420 nm.
Description
Technical field
The present invention relates to as useful light solidifying/heat solidifying resin composition and solidfied material thereof of the printed circuit board (PCB) of forming as necessity with solder resist etc. and the insulating resin layer of various electronic units and the printed circuit board (PCB) that uses its gained, in more detail, relating to maximum wavelength is the light solidifying/heat solidifying resin composition and the solidfied material thereof of the laser generation light source curing gained of 350～420nm, and the printed circuit board (PCB) that uses its gained.
Background technology
Outermost layer at the printed circuit board (PCB) of e-machine is formed with the solder resist film.So-called solder resist film is the surface that covers printed circuit board (PCB), prevent that with scolder lining, the real dress of parts the time protection that circuit surface adheres to unnecessary scolder is coated with cover material.In addition, forever protecting mask is following filming, promptly; the conductor circuit of protection printed circuit board (PCB) is avoided humidity, dust etc.; and have simultaneously and guard the insulator function that circuit is avoided electrical interference, chemical proofing, excellent heat resistance, and the height that also can bear when welding is warm, gold-plated.Formation method as solder resist, usually use following photoetching (photolithography) method, that is, on substrate, form filming of light solidifying/heat solidifying resin composition, and the photomask of the exposing patterns by being formed with regulation shines active energy beam to it, thereby forms pattern.
In recent years, as resource-saving or economize the photoetching process of the consideration environment of energy, practical is in directly the describe mode (laser directly describe) of laser as light source.Directly drawing apparatus is meant: on the printed base plate that forms the film of the Photocurable resin composition of laser sensitization, directly describe the device of laser at a high speed according to pattern data.This device has the advantages that not need mask pattern, can shorten manufacturing process and significantly reduces cost, and is to be suitable for many kinds small batch, the method for short delivery period.
Directly drawing apparatus exposes exposure portion because of can't exposing as mask pattern in the past comprehensively simultaneously, thereby can select exposure portion, unexposed portion that the optical gate switch of laser is exposed successively.Therefore, in order to obtain and the equal time shutter of in the past mask pattern exposure, must under high speed, expose.And then, employed light source is the wide light source to 300～500nm of metal halide lamp equiwavelength in the optical mask pattern exposure in the past, with respect to this, directly in the situation of drawing apparatus, light source and wavelength change because of the purposes of used Photocurable resin composition, usually light source uses semiconductor laser, and its wavelength uses near 350～370nm or near 400～420nm mostly.
But,, also can't form and can obtain filming of the desired thermotolerance of solder resist, insulativity even the direct drawing apparatus that uses wavelength 350～370nm or 400～420nm exposes in the past solder resist.Its reason can be enumerated: the Photoepolymerizationinitiater initiater that solder resist added in the past uses benzil, benzoin ether, michler's ketone, anthraquinone, acridine, azophenlyene, benzophenone, α-acetophenone series initiators, these initiating agents are low to the absorption of 350～370nm or 400～420nm wavelength light, it is abundant that only single wavelength light can not make the photopolymerization initiating power, needs very many time shutter.Therefore, contain the Photocurable composition of Photoepolymerizationinitiater initiater in the past, its range of application is significantly limited.
So, even proposed the composition (for example, with reference to TOHKEMY 2001-235858 communique, international open WO02/096969 communique) that single wavelength light only also can be brought into play the Photoepolymerizationinitiater initiater of high photopolymerization ability and use this Photoepolymerizationinitiater initiater.But, though these technology only also can be brought into play sufficient photopolymerization ability with single wavelength light really, but can't obtain deep curable and surface cure simultaneously, and, because of the Photoepolymerizationinitiater initiater inactivation on the circuit after the thermal treatment causes light sensitivity significantly to reduce, has the problem of the possibility that generation is peeled off on copper circuit.
In addition, directly describe to form portrait, under atmospheric environment gas, carry out usually with laser, so be obstructed because of oxygen induces reaction easily, therefore, after exposure, remove in the development step that does not need part, the solder resist surface element of necessary part is removed, and the result has the problem that causes that easily gloss is bad.And then; at the protection printed circuit board (PCB) is in the solder resist of purpose, and gloss is bad not only to be the problem of bad order, and because the reaction of the part that should react was insufficient originally; thereby its surface of filming is that chemical proofing is poor, and also causes the problem of electrical characteristics difference.
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and to bring into play high photopolymerization ability and to obtain the light solidifying/heat solidifying resin composition of sufficient deep curable and then good heat stability the laser of 350～420nm, particularly be suitable for the solder resist purposes, in addition, be suitable for light solidifying/heat solidifying resin composition and the solidfied material of directly describing with the laser of 350～420nm thereof and use it to form the printed circuit board (PCB) of pattern.
The method that is used to deal with problems
In order to reach aforementioned purpose, according to the present invention, a kind of light solidifying/heat solidifying resin composition can be provided, said composition contains (A) carboxylic resin, (B) the oxime ester that contains the oxime ester base shown in the following general formula (I) is a Photoepolymerizationinitiater initiater, (C) aminoacetophenone with structure shown in the following general formula (II) is that Photoepolymerizationinitiater initiater (C-1) and/or the phosphine oxide that contains structure shown in the following general formula (III) are Photoepolymerizationinitiater initiater (C-2), (D) has the compound of 2 above ethylenically unsaturated groups in the molecule, (E) filling agent, reach (F) Thermocurable composition, and said composition can be developed by diluted alkaline solution, can be that the laser generation light source of 350nm～420nm solidifies by maximum wavelength.
(in the formula, R
1Be the alkyl or the phenyl of 1～7 of expression hydrogen atom, carbon number, R
2Be the alkyl or the phenyl of 1～7 of expression carbon number, R
3, R
4Be the alkyl or the aralkyl of 1～12 of expression carbon number, R
5, R
6Be the alkyl of 1～6 of expression hydrogen atom, carbon number, or R
5And R
6The ring-type alkane ether that the carbon number of be combined into is 4, R
7, R
8For the alkyl of the straight or branched of 1～6 of carbon number of expression, cyclohexyl, cyclopentyl, aryl, by aryl or any one acyl group that halogen atom, alkyl or alkoxy replaced) for 1～20 of expression carbon number.
With the oxime ester that contains the oxime ester base shown in the aforementioned formula (I) be Photoepolymerizationinitiater initiater (B) combination, the aminoacetophenone that has structure shown in the aforementioned formula (II) according to use is which of Photoepolymerizationinitiater initiater (C-2) Photoepolymerizationinitiater initiater (C-1) or the phosphine oxide that contains structure shown in the aforementioned formula (III) are, to the absorbing wavelength difference of laser.When the aminoacetophenone that use has a structure shown in the aforementioned formula (II) is Photoepolymerizationinitiater initiater (C-1), the light solidifying/heat solidifying resin composition of gained can be that the laser generation light source of 350～370nm solidifies by maximum wavelength, on the other hand, when the phosphine oxide that use contains structure shown in the aforementioned formula (III) is Photoepolymerizationinitiater initiater (C-2), can be that the laser generation light source of 400～420nm solidifies by maximum wavelength.In addition, by using these both, can be that the laser generation light source of 350～420nm solidifies then by maximum wavelength.
Therefore, in a specific form of the present invention, a kind of light solidifying/heat solidifying resin composition is provided, said composition contains (A) carboxylic resin, (B) the oxime ester that contains the oxime ester base shown in the aforementioned formula (I) is a Photoepolymerizationinitiater initiater, (C-1) aminoacetophenone with structure shown in the aforementioned formula (II) is a Photoepolymerizationinitiater initiater, (D) has the compound of 2 above ethylenically unsaturated groups in the molecule, (E) filling agent, reach (F) Thermocurable composition, and said composition can be developed by diluted alkaline solution, can be that the laser generation light source of 350～370nm solidifies by maximum wavelength.
In addition, in other specific modality of the present invention, a kind of light solidifying/heat solidifying resin composition is provided, said composition contains (A) carboxylic resin, (B) the oxime ester that contains the oxime ester base shown in the aforementioned formula (I) is a Photoepolymerizationinitiater initiater, (C-2) phosphine oxide that contains structure shown in the aforementioned formula (III) is a Photoepolymerizationinitiater initiater, (D) has the compound of 2 above ethylenically unsaturated groups in the molecule, (E) filling agent, reach (F) Thermocurable composition, and said composition can be developed by diluted alkaline solution, can be that the laser generation light source of 400～420nm solidifies by maximum wavelength.
The form that provides of light solidifying/heat solidifying resin composition of the present invention can be liquid form, in addition, also can be the form of photosensitive dry film.
In addition, according to the present invention, can provide and make light solidifying/heat solidifying resin composition as the aforementioned is the laser curing of 350～420nm or the further solidfied material that obtains of heat curing and the printed circuit board (PCB) that pattern coating film was become that forms this solidfied material with wavelength.
The invention effect
Light solidifying/heat solidifying resin composition of the present invention is that the deep curable is good and can be the pattern that the laser generation light source of 350～420nm forms no halation, undercutting by wavelength, can be used as laser and directly describes to use solder resist.
And then, directly describe to use solder resist by using this type of laser, then can not need the minus pattern, help to improve initial production, the cost degradation of printed circuit board (PCB).
In addition, light solidifying/heat solidifying resin composition of the present invention, because the deep curable is good, ISO and high-resolution are forthright, so can provide fiduciary level high printed circuit board (PCB).
Description of drawings
Fig. 1 is the cross sectional shape synoptic diagram of the pattern coating film of the light solidifying/heat solidifying resin composition that obtains with exposure imaging.
Symbol description
1: substrate
2: pattern coating film
L: the design load of live width
Embodiment
The present inventor is in order to reach the result that aforementioned purpose is endeavoured to study, discovery is containing (A) carboxylic resin, (D) has the compound of 2 above ethylenically unsaturated groups in the molecule, (E) filling agent, reach in the light solidifying/heat solidifying resin composition of (F) Tong Guo the diluted alkaline property solution development of Thermocurable composition, being used in combination the oxime ester that (B) contain the oxime ester base shown in the aforementioned formula (I) is Photoepolymerizationinitiater initiater, (C) aminoacetophenone with structure shown in the aforementioned formula (II) is that Photoepolymerizationinitiater initiater (C-1) and/or the phosphine oxide that contains structure shown in the aforementioned formula (III) are that Photoepolymerizationinitiater initiater (C-2) is during as Photoepolymerizationinitiater initiater, can bring into play high photopolymerization ability to the laser of 350～420nm, and obtain sufficient deep curable, and further obtain the composition of good heat stability, and until finishing the present invention.In addition, by with the oxime ester that contains the oxime ester base shown in the aforementioned formula (I) be Photoepolymerizationinitiater initiater combination, and to use the aminoacetophenone with structure shown in the aforementioned formula (II) be that Photoepolymerizationinitiater initiater (C-1) or the phosphine oxide that contains structure shown in the aforementioned formula (III) are any one of Photoepolymerizationinitiater initiater (C-2), then to the absorbing wavelength difference of laser.When the aminoacetophenone that use has a structure shown in the aforementioned formula (II) is Photoepolymerizationinitiater initiater (C-1), the light solidifying/heat solidifying resin composition of gained can be that the laser generation light source of 350～370nm solidifies by maximum wavelength, on the other hand, when the phosphine oxide that use contains structure shown in the aforementioned formula (III) is Photoepolymerizationinitiater initiater (C-2), can be that the laser generation light source of 400～420nm solidifies by maximum wavelength.In addition, by using both, can be that the laser generation light source of 350～420nm solidifies then by maximum wavelength.And then, even using the aminoacetophenone with structure shown in the aforementioned formula (II) is that Photoepolymerizationinitiater initiater (C-1) or the phosphine oxide that contains structure shown in the aforementioned formula (III) are when being any one of Photoepolymerizationinitiater initiater (C-2), also can be by adding other Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, and adjustment is to the absorbing wavelength of laser, when particularly using aminoacetophenone to be Photoepolymerizationinitiater initiater (C-1) with structure shown in the aforementioned formula (II), by adding thioxanthones is Photoepolymerizationinitiater initiater, then can adjust absorbing wavelength, and be that the laser generation light source of 350～370nm solidifies with maximum wavelength to laser.
Below, describe each constituent in detail about light solidifying/heat solidifying resin composition of the present invention.
The contained carboxy resin (A) that contains can use the resin compound known commonly used that has carboxyl in the molecule in the light solidifying/heat solidifying resin composition of the present invention.And then from photo-curable, anti-development aspect, what more preferably have ethylenical unsaturated double bonds in the molecule contains carboxyl photoresist (A ').
The concrete example that contains carboxy resin can be listed below states listed resin.
Can enumerate:
(1) carboxylic copolymer resins, it is for by making unsaturated carboxylic acid such as (methyl) acrylic acid, obtaining with more than one copolymerization of the compound with unsaturated double-bond beyond it.
(2) photosensitive carboxylic copolymer resins, its for by make unsaturated carboxylic acid such as (methyl) acrylic acid with its beyond the multipolymer that has the compound of unsaturated double-bond more than a kind, and (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters etc. has reactions such as the compound of epoxy radicals and unsaturated double-bond or (methyl) acryloyl chloride, thereby ethylenically unsaturated group is obtained as the side group addition.
(3) photosensitive carboxylic copolymer resins, it is for making (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters etc. has the compound of epoxy radicals and unsaturated double-bond and the multipolymer of the compound with unsaturated double-bond beyond it, with the reaction of unsaturated carboxylic acid such as (methyl) acrylic acid, the secondary hydroxyl that is generated is reacted with multi-anhydride and obtain.
(4) photosensitive carboxylic copolymer resins, it is to make maleic anhydride etc. have the acid anhydrides of unsaturated double-bond and the multipolymer of the compound with unsaturated double-bond beyond it, has the compound reaction of hydroxyl and unsaturated double-bond with (methyl) acrylic acid 2-hydroxyl ethyl ester etc. and obtains.
(5) carboxylic photoresist, it makes saturated or unsaturated multi-anhydride obtain with the hydroxyl reaction that is generated for making the reaction of multi-functional epoxy compound and unsaturated monocarboxylic acid.
(6) contain the photoresist of hydroxyl and carboxyl, it makes the compound that has epoxy radicals and unsaturated double-bond in a part be obtained with the carboxylic acid reaction that generates for making the reaction of hydroxyl polymer-containing such as polyvinyl alcohol derivative and saturated or unsaturated multi-anhydride then.
(7) carboxylic photoresist, its for multi-functional epoxy compound, unsaturated monocarboxylic acid, with a part in have at least 1 alcoholic extract hydroxyl group and with the alcoholic extract hydroxyl group of epoxy reaction beyond the reaction product of compound of 1 reactive group, with saturated or unsaturated multi-anhydride reaction and obtain.
(8) carboxylic photoresist, it is to make multifunctional oxetane compound and the unsaturated monocarboxylic acid reaction that has at least 2 oxetanes rings in a part, make the primary hydroxyl reaction in the modification oxetane resin of saturated or unsaturated multi-anhydride and gained and obtain, and
(9) carboxylic photoresist, it is for making the reaction of polyfunctional epoxy resin and unsaturated monocarboxylic acid, make the multi-anhydride reaction then, obtain containing the carboxyl photoresist with this, make it have the compound reaction of 1 oxirane ring and 1 above ethylenically unsaturated group and obtain again with in the molecule, Deng
But be not limited to these.
Preferred resin is the carboxy resin that contains of above-mentioned (2), (5), (7), (9) in the middle of these illustrations, from photo-curable, cured coating film characteristic aspect, especially preferably above-mentioned (9) contain the carboxyl photoresist.
In addition, in the present invention, so-called (methyl) acrylate is the term with acrylate, methacrylate and composition thereof general name, and it also is same similarly explaining about other.
As above-mentioned carboxylic resin (A),, can develop by the diluted alkaline aqueous solution owing on the side chain of trunk polymer, have many free carboxyls.
In addition, the expectation of the acid number of above-mentioned carboxylic resin (A) is the scope of 40～200mgKOH/g, more preferably the scope of 45～120mgKOH/g.If the acid number of carboxylic resin is not enough 40mgKOH/g, then be difficult to alkaline development, on the other hand, if surpass 200mgKOH/g, then because of the expose dissolving of portion of developer solution, so line is thinner than needed, according to circumstances, exposed portion and unexposed portion indistinction ground dissolve in developer solution to be peeled off, and difficulty is depicted normal solder resist pattern, so not preferred.
In addition, the weight-average molecular weight of above-mentioned carboxylic resin (A) is generally 2000～150000 for different according to resin matrix, more preferably 5000～100000 scope.If weight-average molecular weight is less than 2000, then poor to the coating of substrate, dried tack-free property, in addition, the moisture-proof of filming after the exposure is poor, produces the film attenuate when developing, and resolution is variation greatly.On the other hand, if weight-average molecular weight is for surpassing 150000, the remarkable variation of development property then, storage-stable is poor.
The use level expectation of this type of carboxylic resin (A) is preferably 30～50 quality % for the scope of 20～60 quality % of whole composition.When the use level of carboxylic resin (A) is less than above-mentioned scope, because of coating strength reduces, so not preferred.On the other hand, if during more than above-mentioned scope, then the viscosity of composition uprises, and coating reduces, so not preferred.
The used oxime ester of the present application is Photoepolymerizationinitiater initiater (B), for the oxime ester that contains the oxime ester base shown in the following general formula (I) is a Photoepolymerizationinitiater initiater, can enumerate the material that for example aforementioned TOHKEMY 2001-235858 communique is put down in writing.
(in the formula, R
1Be the alkyl or the phenyl of 1～7 of expression hydrogen atom, carbon number, R
2Alkyl or phenyl for 1～7 of expression carbon number)
This type of oxime ester is that Photoepolymerizationinitiater initiater (B) preferred substance is the 2-shown in the following formula (IV) (acetoxyl group iminomethyl) thioxanthene-9-one, and commercially available product can be enumerated the CGI-325 of Xiba Special Chemical Product Co.,Ltd's system.
And then, be fit to use shown in the following formula (V)
1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } and 1, the trade name Irgacure-OXE01 of 2-acetyl caproyl, Xiba Special Chemical Product Co.,Ltd's system and following formula (VI)
Shown 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-the trade name Irgacure-OXE02 of 1-(O-acetyl oxime) ethyl ketone, Xiba Special Chemical Product Co.,Ltd's system etc.
The light solidifying/heat solidifying resin composition that to contain this type of oxime ester be Photoepolymerizationinitiater initiater (B), when being applied on the copper of printed circuit board (PCB) etc. separately, with the interface of copper and copper atom by temporary transient thermal response when dry, has the functionally inactive that makes as Photoepolymerizationinitiater initiater (if heating then can't photopolymerization on copper, and poor heat stability.) problem.Therefore, among the present invention, must and use the aminoacetophenone with structure shown in the aforementioned formula (II) is that Photoepolymerizationinitiater initiater (C-1) and/or the phosphine oxide that contains structure shown in the aforementioned formula (III) are Photoepolymerizationinitiater initiater (C-2).
This type of oxime ester is that the use level of Photoepolymerizationinitiater initiater (B) is the ratio of 0.01～10 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A) expectation, and being preferably is the ratio of 0.01～5 mass parts.The oxime ester is that the use level of Photoepolymerizationinitiater initiater (B) is during with respect to the aforementioned carboxylic resins of 100 mass parts (A) less than 0.01 mass parts, the light of 350～420nm wavelength region may is abundant inadequately to the curing of photonasty composition (compound (D) that has 2 above ethylenically unsaturated groups in the illustrative carboxylic photoresist of aforementioned (A) composition, the molecule described later), the hydroscopicity of cured coating film uprises and the PCT tolerance easily reduces, in addition, the also easy step-down of solder heat resistance, anti-electroless plating.On the other hand, the oxime ester is the use level of Photoepolymerizationinitiater initiater (B), when surpassing 20 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A), the anti-electroless plating variation of the development of filming, cured coating film, and the PCT tolerance also shows the tendency of variation.
Aminoacetophenone with structure shown in the following general formula (II) used in the present invention is Photoepolymerizationinitiater initiater (C-1), can enumerate for example 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine amido acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-ketone, N, N-dimethylamino acetophenone etc.Commercially available product can be enumerated Irgacure 907, the Irgacure 369 etc. of Xiba Special Chemical Product Co.,Ltd's system.
(in the formula, R
3, R
4Be the alkyl or the aralkyl of 1～12 of expression carbon number, R
5, R
6Alkyl or R for 1～6 of expression hydrogen atom, carbon number
5With R
6The ring-type alkane ether that the carbon number of be combined into is 4.)
This type of aminoacetophenone is Photoepolymerizationinitiater initiater (C-1) polymerization that can not hinder aforementioned oxime ester be Photoepolymerizationinitiater initiater (B), and then, by the photo-curable that to remedy aforementioned oxime ester be Photoepolymerizationinitiater initiater (B) with the interface inactivation of copper the time, thereby on copper, also can give sufficient photo-curable.
This type of aminoacetophenone is that the use level of Photoepolymerizationinitiater initiater (C-1) is the ratio of 0.1～30 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A) expectation, is preferably the ratio of 0.5～15 mass parts.Aminoacetophenone is that the use level of Photoepolymerizationinitiater initiater (C-1) is during with respect to the aforementioned carboxylic resins of 100 mass parts (A) less than 0.1 mass parts, the photo-curable deficiency of the light solidifying/heat solidifying resin composition of gained on copper, and film and peel off, the coating characteristic of chemical proofing etc. reduces, so not preferred.On the other hand, aminoacetophenone is that the use level of Photoepolymerizationinitiater initiater (C-1) is when surpassing 30 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A), because aminoacetophenone is the light absorption of Photoepolymerizationinitiater initiater (C-1), the deep curable reduces, so not preferred.
Phosphine oxide with structure shown in the following general formula (III) used in the present invention is Photoepolymerizationinitiater initiater (C-2); for example can enumerate 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2; 4,4-trimethyl-amyl group phosphine oxide etc.
(in the formula, R
7, R
8For the alkyl of the straight or branched of 1～6 of carbon number of expression, cyclohexyl, cyclopentyl, aryl, by aryl or any one acyl group (being preferably benzoyl) that halogen atom, alkyl or alkoxy replaced with 2～12 alkyl of carbon number for 1～20 of carbon number.)。
This type of phosphine oxide is Photoepolymerizationinitiater initiater (C-2) polymerization that can not hinder aforementioned oxime ester be Photoepolymerizationinitiater initiater (B), and then, by the photo-curable that to remedy aforementioned oxime ester be Photoepolymerizationinitiater initiater (B) with the interface inactivation of copper the time, thereby on copper, also can give sufficient photo-curable.
This type of phosphine oxide is that the use level of Photoepolymerizationinitiater initiater (C-2) is the ratio of 0.05～20 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A) expectation, is preferably the ratio of 0.1～10 mass parts.Phosphine oxide is that the use level of Photoepolymerizationinitiater initiater (C-2) is when surpassing 20 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A), photo-curable during the thick film of the light solidifying/heat solidifying resin composition of gained reduces, cause the expense of product to rise, so not preferred.
In addition, oxime shown in the aforementioned formula (I) be aminoacetophenone that the use level ratio of Photoepolymerizationinitiater initiater (B) has a structure shown in the aforementioned formula (II) be the phosphine oxide shown in Photoepolymerizationinitiater initiater (C-1), the aforementioned formula (III) be Photoepolymerizationinitiater initiater (C-2) use level after a little while, because it is can obtain ISO and thick film curable, so preferred.
In addition, aminoacetophenone with structure shown in the aforementioned formula (II) is Photoepolymerizationinitiater initiater (C-1), to aforementioned oxime ester is that Photoepolymerizationinitiater initiater (B) inactivation on Copper Foil plays useful effect, but, be that Photoepolymerizationinitiater initiater (C-2) can play useful effect so contain the phosphine oxide of structure shown in the aforementioned formula (III) owing to independent laser for 400～420nm does not have absorbing wavelength.Be that Photoepolymerizationinitiater initiater (B) is Photoepolymerizationinitiater initiater (C-2) with above-mentioned phosphine oxide so, preferably to the laser of 400～420nm and with aforementioned oxime ester.And then, from aspects such as surface cures, be Photoepolymerizationinitiater initiater (C-1) more preferably and with aminoacetophenone.When making up these aminoacetophenones and be Photoepolymerizationinitiater initiater (C-1) and being Photoepolymerizationinitiater initiater (C-2) with phosphine oxide, its ratio is not particularly limited, but the absorbance when preferably fitting in used Wavelength of Laser zone dry coating 25 μ m is 0.3～1.5.
Light solidifying/heat solidifying resin composition of the present invention also can be as required with benzoin and benzoin alkane ethers such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylethers; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1, acetophenones such as 1-dichloroacetophenone; Anthraquinone classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2-isopropyl thioxanthone, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones; Ketal classes such as acetophenone dimethyl ketal, benzil dimethyl ketal; Benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-benzophenone or xanthene ketones such as propyl group diphenyl sulfide; 2,4, the Photoepolymerizationinitiater initiater known commonly used of phosphinoxidess such as 6-trimethylbenzoyl diphenyl phosphine oxide etc. and aforementioned lights polymerization initiator (B) reach (C-1) and/or (C-2) also use.Particularly preferred also with 2 from curable aspect, deep, 4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2-isopropyl thioxanthone, 2, thioxanthones such as 4-diisopropyl thioxanthones are Photoepolymerizationinitiater initiater.
In addition, light solidifying/heat solidifying resin composition of the present invention can contain tertiary amine compound, benzophenone cpd as light-initiated auxiliary agent.This type of tertiary amines can be enumerated ethanolamines, 4,4 '-dimethylamino benzophenone (Japanese Cao Da corporate system NissoCure MABP), 4-dimethylamino ethyl benzoate (Japanese chemical drug corporate system Kayacure EPA), 2-dimethylamino ethyl benzoate (InternationalBiosynthetics corporate system Quantacure DMB), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (International Biosynthetics corporate system QuantacureBEA), right-dimethylamino benzoic acid isopentyl ethyl ester (Japanese chemical drug corporate system Kayacure DMBI), 4-dimethylamino benzoic acid 2-Octyl Nitrite (Van Dyk corporate system Esolol 507), 4,4 '-diethylamino benzophenone (the system EAB of hodogaya chemical industrial group) etc.These known tertiary amine compounds commonly used can use separately or as the potpourri more than two kinds.Particularly preferred tertiary amine compound is 4,4 '-the diethylamino benzophenone, but be not particularly limited to these, as long as in the regional absorbing light of wavelength 350～420nm and by also using the material of bringing into play the sensitization effect with the hydrogen-abstraction Photoepolymerizationinitiater initiater, then be not limited to Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, can separately or and use several.Be preferably 4,4 herein especially '-diethylamino benzophenone (the system EAB of hodogaya chemical industrial group).
The use level of this type of Photoepolymerizationinitiater initiater and photopolymerization auxiliary agent for aforementioned oxime ester be that Photoepolymerizationinitiater initiater (B) and aminoacetophenone are that Photoepolymerizationinitiater initiater (C-1) and/or phosphine oxide are the total amount of Photoepolymerizationinitiater initiater (C-2), with respect to the aforementioned carboxylic resins of 100 mass parts (A), be the following scopes of 35 mass parts, and then, in the composition that contains the aftermentioned coloring pigment, its dry coating is 0.3～1.5, more preferably 0.5～1.2 scope when the absorbance of wavelength 355nm or 405nm is preferably thickness 25 μ m.Under the situation of Duoing than above-mentioned scope, because its light absorption, the deep curable of the light solidifying/heat solidifying resin composition of gained reduces easily, and than under the little situation of above-mentioned scope, surface cure is poor, and easy halation, so not preferred.
The compound (D) that has two above ethylenically unsaturated groups in the used molecule of light solidifying/heat solidifying resin composition of the present invention, for by active energy beam irradiation photocuring, make aforementioned carboxylic resin (A) insoluble or help thawless material in alkaline aqueous solution.The concrete example of this compounds can be enumerated hydroxyalkyl acrylate classes such as acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate; The list or the diacrylate class of dibasic alcohol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol; N,N-DMAA, N hydroxymethyl acrylamide, N, acrylic amides such as N-dimethylaminopropyl acrylamide; Acrylic acid N, N-dimethylamino ethyl ester, acrylic acid N, acrylic-amino alkyl esters such as N-dimethylamino propyl ester; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or its ethylene oxide adduct or propylene oxide adduct etc.; The esters of acrylic acid of phenoxy group acrylate, bisphenol a diacrylate, the ethylene oxide adduct that reaches these phenols or propylene oxide adduct etc.; The esters of acrylic acid of glycidol ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; And melamine acrylate and/or pairing each methyl acrylic ester of aforesaid propylene acid esters etc.
And then, can enumerate the Epocryl that obtains of polyfunctional epoxy resins such as making the cresols phenolic resin varnish type epoxy resin and acrylic acid reaction, and half urethane compounds of diisocyanate such as hydroxy acrylate such as the hydroxyl that makes this Epocryl again and pentaerythritol triacrylate and isophorone diisocyanate is reacted the epoxy urethanes acrylate compounds that obtains etc.This type of epoxy acrylate is the dry to touch reduction of the dry coating of the resin light solidifying/heat solidifying resin composition that can not make gained, and can improve photo-curable.
The use level that has the compound (D) of two above ethylenically unsaturated groups in this quasi-molecule is the ratio of 5～100 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A) expectation, more preferably the ratio of 1～70 mass parts.Aforementioned use level is during with respect to the aforementioned carboxylic resins of 100 mass parts (A) less than 5 mass parts, the photo-curable of the light solidifying/heat solidifying resin composition of gained reduces, and it is difficult by the postradiation alkaline development formation of active energy beam pattern, so not preferred.On the other hand, when surpassing 100 mass parts, to the dissolubility reduction of alkaline aqueous solution, filming becomes fragile, so not preferred.
Filling agent used in the present invention (E) can use known inorganic or organic filler commonly used, especially preferably uses barium sulphate, spherical silicon dioxide.And then, also can use NANORYL (trade name) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (being the product type name), NANOPOX (trade name) XP 0516 of Hanse-Chemie corporate system, XP 0525, the XP 0314 (being the product type name) of the Hanse-Chemie corporate system of the compound (D) that in aforementioned molecule, has two above ethylenically unsaturated groups, multi-functional epoxy compound described later (F-1) dispersing nanometer silicon dioxide.
These filling agents (E) can separately or cooperate more than 2 kinds, and the cure shrinkage that can suppress to film improves fundamental characteristics such as adaptation, hardness.
The use level of these filling agents (E) is 0.1～200 mass parts with respect to the aforementioned carboxylic resins of 100 mass parts (A), is preferably the ratio of 1～100 mass parts.The use level of aforementioned filling agent (E) is during with respect to the aforementioned carboxylic resins of 100 mass parts (A) less than 0.1 mass parts, and cured coating film characteristics such as the solder heat resistance of the light solidifying/heat solidifying resin composition of gained, gold-plated tolerance reduce, so not preferred.On the other hand, when surpassing 200 mass parts, the viscosity of composition uprises and printing reduces, and solidfied material becomes fragile, so not preferred.
The Thermocurable composition (F) that the present invention is used can use known heat-curing resins commonly used such as amino resins such as melamine resin, benzoguanamine resin, block isocyanate compound, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxetane compound, episulfide resin.Wherein, have in preferred especially multi-functional epoxy compound (F-1), multifunctional oxetane compound (F-2), the episulfide resin equimolecular two above ring-type ethers and/or cyclic thioether base the Thermocurable composition (below, abbreviate ring-type (sulphur) ether compound as.)。
Aforementioned multi-functional epoxy compound (F-1) can use for example EPIKOTE 828 of Japan EpoxyResin corporate system, EPIKOTE 834, EPIKOTE 1001, EPIKOTE 1004, the EPICLON 840 of big Japanese ink chemical industrial company system, EPICLON 850, EPICLON 1050, EPICLON 2055, Dongdu changes into the Epo Tohto YD-011 of corporate system, YD-103, YD-127, YD-128, the D.E.R.317 of DowChemical corporate system, D.E.R.331, D.E.R.661, the ARALDITE 6071 of D.E.R.664-Xiba Special Chemical Product Co.,Ltd, ARALDITE6084, ARALDITE GY250, ARALDITE GY260, the Sumi-epoxy ESA-011 of Sumitomo Chemical Co. Ltd.'s system, ESA-014, ELA-115, ELA-128, the A.E.R.330 of industrial group of Asahi Chemical Industry system, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin; The EPIKOTE YL903 of Japan Epoxy Resin corporate system, the EPICLON 152 of big Japanese ink chemical industrial company system, EPICLON 165, Dongdu changes into the Epo TohtoYDB-400 of corporate system, YDB-500, the D.E.R 542 of Dow Chemical corporate system, the ARALDITE 8011 of Xiba Special Chemical Product Co.,Ltd's system, the Sumi-epoxy ESB-400 of Sumitomo Chemical Co. Ltd.'s system, ESB-700, the A.E.R.711 of industrial group of Asahi Chemical Industry system, A.E.R.714 etc. (being trade name) brominated epoxy resin; The EPIKOTE 152 of Japan EpoxyResin corporate system, EPIKOTE 154, the D.E.N.431 of Dow Chemical corporate system, D.E.N.438, the EPICLON N-730 of big Japanese ink chemical industrial company system, EPICLON N-770, EPICLON N-865, Dongdu changes into the Epo Tohto YDCN-701 of corporate system, YDCN-704, the ARALDITE ECN 1235 of Xiba Special Chemical Product Co.,Ltd's system, ARALDITE ECN 1273, ARALDITE ECN 1299, ARALDITE XPY 307, the EPPN-201 of Japan's chemical drug corporate system, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the Sumi-epoxy ESCN-195X of Sumitomo Chemical Co. Ltd.'s system, ESCN-220, the A.E.R.ECN-235 of industrial group of Asahi Chemical Industry system, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin; (being trade name) bisphenol f type epoxy resins such as ARALDITE XPY 306 of EPICLON 830, the Japan Epoxy Resin corporate system EPIKOTE 807 of big Japanese ink chemical industrial company system, the Epo Tohto YDF-170 that Dongdu changes into corporate system, YDF-175, YDF-2004, Xiba Special Chemical Product Co.,Ltd's system; Dongdu changes into Epo Tohto ST-2004, ST-2007, the ST-3000 bisphenol-A epoxy resins such as (trade names) of corporate system; (being trade name) glycidyl amine type epoxy resins such as Sumi-epoxy ELM-120 of the EpoTohto YH-434 that the EPIKOTE 604 of JapanEpoxy Resin corporate system, Dongdu change into corporate system, the ARALDITE MY720 of Xiba Special Chemical Product Co.,Ltd's system, Sumitomo Chemical Co. Ltd.'s system; The ARALDITECY-350 of Xiba Special Chemical Product Co.,Ltd's system hydantoins type epoxy resin such as (trade names); Daicel ChemicalIndustries, ARALDITE CY175, CY179 (the being trade name) alicyclic epoxy resin of the Celloxide 2021 of Ltd. system, Xiba Special Chemical Product Co.,Ltd's system; (being trade name) trihydroxy benzene methylmethane type epoxy resin such as the YL-933 of Japan Epoxy Resin corporate system, T.E.N., the EPPN-501 of Dow Chemical corporate system, EPPN-502; Two xylenol types such as YL-6056, the YX-4000 of Japan Epoxy Resin corporate system, YL-6121 (being trade name) or bisphenol-type epoxy resin or its potpourri; The EXA-1514 bisphenol-s epoxy resins such as (trade names) of the EBPS-200 of Japan's chemical drug corporate system, the EPX-30 of Asahi Electro-Chemical Co. Ltd's system, big Japanese ink chemical industrial company system; The EPIKOTE157S bisphenol-A phenolic varnish type epoxy resin such as (trade names) of Japan Epoxy Resin corporate system; The EPIKOTE YL-931 of Japan Epoxy Resin corporate system, (being trade name) four phenolic hydroxyl group ethane type epoxy resin such as ARALDITE 163 of Xiba Special Chemical Product Co.,Ltd's system; (being trade name) hetero ring type epoxy resin such as TEPIC of the ARALDITE PT810 of Xiba Special Chemical Product Co.,Ltd's system, daily output chemical industrial company system; O-phthalic acid diglycidyl ester resins such as the system BLEMMER DGT of Nof Corp.; Dongdu changes into four glycidyl group xylenols ethane resin such as corporate system ZX-1063; Chemical company of Nippon Steel system ESN-190, ESN-360, big Japanese ink chemical industrial company make the epoxy resin that HP-4032, EXA-4750, EXA-4700 etc. contain naphthyl; Big Japanese ink chemical industrial company makes the epoxy resin that HP-7200, HP-7200H etc. have the bicyclopentadiene skeleton; Glycidyl methacrylate copolymerization such as Nof Corp. system CP-50S, CP-50M are epoxy resin; And the copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxide modified polybutadiene rubber derivant (for example Daicel Chemical Industries, the PB-3600 of Ltd. system etc.), CTBN modified epoxy (for example Dongdu changes into YR-102, the YR-450 etc. of corporate system) etc., but be not limited to these.These epoxy resin can be used alone or in combination more than two kinds.Wherein, preferred especially phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or its potpourri.
Aforementioned multifunctional oxetane compound (F-2), can enumerate two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, multifunctional oxetanes classes such as these oligomer or multipolymer, in addition, also can enumerate oxetanes and novolac resin, poly-(right-hydroxy styrenes), cardo type bisphenols, calixarene kind, the resorcinol aromatic hydrocarbons, or silsesquioxane etc. has the etherate that the resin of hydroxyl forms.Other also can enumerate the multipolymer of unsaturated monomer with oxetanes ring and (methyl) alkyl acrylate etc.
The compound that has two above cyclic thioether bases in the aforementioned molecule can be enumerated bisphenol A-type episulfide resin YL 7000 of Japan Epoxy Resin corporate system for example etc.In addition, also can use same synthetic method that the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced into episulfide resin of sulphur atom etc.
The use level of this type of ring-type (sulphur) ether compound is with respect to 1 equivalent carboxyl of aforementioned carboxylic resin (A), and ring-type (sulphur) ether is 0.6～2.0 equivalent, is preferably the scope of 0.8～1.5 equivalent.When the use level of ring-type (sulphur) ether compound was less than above-mentioned scope, carboxyl was residual, and so reductions such as the thermotolerance of cured coating film, alkali resistance, electrical insulating property are not preferred.On the other hand, when surpassing above-mentioned scope, low-molecular-weight ring-type (sulphur) ether is remaining, makes the reductions such as intensity of cured coating film, so not preferred.
When using above-mentioned ring-type (sulphur) ether compound, preferably contain thermal curing catalyst.This type of thermal curing catalyst can be enumerated for example imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, hydrazine compounds such as amines such as N-dimethyl benzyl amine, adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenylphosphine etc., as commercially available product, for example four countries change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound), U-CAT 3503N, the U-CAT3502T (being the trade name of the block isocyanate compound of dimethyl amine) of SAN-APRO LIMITED system, DBU, DBN, U-CATSA102, the U-CAT5002 (being two ring type amidine compound and salt thereof) etc. of industrial group's system in addition.Particularly, be not limited to these,, can be used alone or as a mixture more than two kinds also harmless as long as be the thermal curing catalyst of epoxy resin, oxetane compound or the material that promotes the reaction of epoxy radicals and/or oxetanyl and carboxyl.In addition, also can use the guanamines, acetylguanamine, benzoguanamine, the melamine, 2 that play a role as the adaptation imparting agent, 4-diamido-6-methylacryoyloxyethyl-s-triazine, 2-vinyl-4,6-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2,4-diamido-6-methylacryoyloxyethyl-Striazine derivatives such as s-triazine isocyanuric acid addition product is preferably compound and aforementioned hot curing catalysts and the usefulness of these also being brought into play the effect of adaptation imparting agent.
The use level of thermal curing catalyst is fully with common deal ratio, with respect to aforementioned carboxylic resins of 100 mass parts (A) or ring-type (sulphur) ether compound, is 0.1～20 mass parts for example, is preferably the ratio of 0.5～15.0 mass parts.
And then light solidifying/heat solidifying resin composition of the present invention is applied to substrate, the required viscosity of carrier film for synthetic aforementioned carboxylic resin (A), modulation group compound or in order to adjust, can be with an organic solvent.
This type of organic solvent can be enumerated ketone, aromatic hydrocarbon based, glycol ethers, glycol ether acetates, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.Example can be enumerated ketones such as MEK, cyclohexanone more specifically; Toluene, dimethylbenzene, tetramethylbenzene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Glycol ether acetates such as dipropylene glycol methyl ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate, propylene glycol monobutyl ether acetate; Ester classes such as the acetic acid carboxylate of ethyl acetate, butyl acetate 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.
This type of organic solvent can use separately or with the potpourri more than two kinds.
Light solidifying/heat solidifying resin composition of the present invention, can cooperate phthalocyanine blue more as required, phthalocyanine green, iodine is green, dual-azo yellow, crystal violet, titanium dioxide, carbon black, known colorants commonly used such as naphthalene is black, quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, 1,2, the 3-benzenetriol, known hot polymerization inhibitor commonly used such as phenothiazine, fine particle silica, organobentonite, known thickening agent commonly used such as smectite, silicone-based, fluorine system, the defoamer of macromolecular etc. and/or levelling agent, imidazoles system, thiazole system, the adaptation imparting agent of triazole system etc., known additive kind commonly used such as silane coupling agent.
Light solidifying/heat solidifying resin composition of the present invention for example is adjusted to the viscosity that is suitable for coating process with aforementioned organic solvent, and be coated with methods such as method, silk screen rubbing method, curtain Tu Fa by dip coating, flow coat method, rolling method, rod and be coated on the substrate, and under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), then can form filming of not touching with one's hand.In addition, above-mentioned composition is applied on the carrier film and drying obtains film, the film of reeling is fitted on the base material, thereby can form resin insulating barrier.
The volatile dry that light solidifying/heat solidifying resin composition coating of the present invention back is carried out, can use heated air circulation type drying oven, IR stove (infrared furnace), electric hot plate, convection furnace etc., and can adopt variety of way, as, use possess with the device of the thermal source of the air heat mode of steam and make the hot blast counter current contacting in the dryer method, blow to the mode of supporter by ozzle etc.
, for the filming of gained expose (irradiation of active energy beam), thereby exposure portion (with the part that active energy beam was shone) is solidified thereafter.
Exposure be for can directly describing according to appointed pattern by laser beam etc., but also can pass through contact (or noncontact mode), sees through the photomask that is formed with the appointment exposing patterns and optionally exposes with active energy beam.
Then, with laser beam etc. directly describe and the situation of exposing in, with regard to the state of its former state (or when using photomask remove photomask back), with diluted alkaline aqueous solution (for example 0.3～3% aqueous sodium carbonate) with unexposed development, thereby can form the resist pattern.And then, be heated to about 140～180 ℃ temperature and make its heat curing, thereby can make Thermocurable composition (F) reactions such as the carboxyl of aforementioned carboxylic resin (A) and ring-type (sulphur) ether compound, form the cured coating film of each characteristic good such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics.
Above-mentioned base material can be enumerated use paper-phenolics composite wood, paper-epoxy resin composite wood, glass cloth-epoxy resin composite wood, glass-polyimide composite wood, glass cloth/nonwoven fabrics-epoxy resin composite wood, glass cloth/paper-epoxy resin composite wood, synthon-epoxy resin composite wood, high-frequency circuits such as fluororesin tygon PPO cyanate composite wood are with the copper clad laminate of whole models (FR-4 etc.) of used various materials such as copper clad laminate, Kapton, the PET film, glass substrate, ceramic substrate, wafer board etc.
Used exposure machine in the irradiation of above-mentioned active energy beam can use direct drawing apparatus (for example by from the cad data of computing machine directly with the direct drawing apparatus of the laser of laser rendering image).As active energy beam, be the laser of 350～420nm scope as long as use maximum wavelength, just can be gas laser, Solid State Laser any one.In addition, its exposure is generally 5～200mJ/cm according to thickness etc. and different
2, be preferably 5～100mJ/cm
2, 5～50mJ/cm more preferably
2Scope in.Above-mentioned direct drawing apparatus can use for example Japanese Orbotech corporate system, the Via of Hitachi corporate system, Pentax corporate system etc., as long as for to send the device that maximum wavelength is the laser of 350～420nm, then any device all can use.
Aforementioned developing method can use infusion process, spray process, gunite, brushing method etc., and developer solution can use the alkaline aqueous solution of potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.Alkali concn in the developer solution is approximately 0.1～5wt% and gets final product.
The radiation source of above-mentioned active energy beam is except can be various laser beams, and low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, metal halide lamp etc. also are suitable.In addition, also can utilize electron beam, alpha ray, β ray, gamma-rays, X ray, neutron beam etc.
[embodiment]
Below embodiment is shown and comparative example specifies the present invention, but the present invention is not defined to following embodiment certainly.
Synthesis example 1
In 2 liters of separate type flasks that possess stirring machine, thermometer, backflow cooling tube, tap funnel and nitrogen ingress pipe, import cresols phenolic resin varnish type epoxy resin (Japanese chemical drug (strain) system, EOCN-104S, 92 ℃ of softening points, epoxide equivalent 220) 660 grams, carbitol acetate 421.3 gram, and solvent naphtha 180.6 grams, and heating, be stirred to 90 ℃, dissolving.Then, this resin solution temporarily is cooled to 60 ℃, adding acrylic acid 216 grams, triphenylphosphine 4.0 grams, methylnaphthohydroquinone 1.3 grams, and under 100 ℃, reacted 12 hours, obtain the reaction product that acid number is 0.2mgKOH/g.To wherein adding tetrabydrophthalic anhydride 241.7 grams, be heated to 90 ℃, make its reaction 6 hours.Obtain the solution of the carboxylic resin (A) of acid number 50mgKOH/g, two key equivalent (gram weight of the resin of per 1 mole of unsaturated group) 400, weight-average molecular weight 7000 thus.Below, this carboxylic resin solution is called A-1 varnish.
Synthesis example 2
In 2 liters of separate type flasks that possess stirring machine, thermometer, backflow cooling tube, tap funnel and nitrogen ingress pipe, the o-cresol phenolic epoxy varnish of packing into (on average having 6 phenol nucleus in epoxide equivalent 215,1 molecule) 430 grams and acrylic acid 144 grams (2 moles).This reaction mixture is heated to 120 ℃ while stirring, and remains on 120 ℃ of continuation reactions 10 hours.Temporarily reaction product is cooled to room temperature, adds succinic anhydride 190 grams (1.9 moles), and be heated to 80 ℃ and make its reaction 4 hours.Once again this reaction product is cooled to room temperature.The acid number of this product solid constituent is 139mgKOH/g.
In this solution, add glycidyl methacrylate 85.2 grams (0.6 mole) and 1-Methoxy-2-propyl acetate 45.9 grams, be heated to 110 ℃, and remain on 110 ℃ of continuation reactions 6 hours while stir.When this reaction product is cooled to room temperature, obtain the solution of thickness.So handle, obtain the solution of the carboxylic resin (A) of nonvolatile component 65 quality %, solid constituent acid number 86mgKOH/g.Below, this carboxylic resin solution is called A-2 varnish.
Synthesis example 3
In 2 liters of separate type flasks that possess stirring machine, thermometer, backflow cooling tube, tap funnel and nitrogen ingress pipe, (big Japanese ink chemical industry (strain) is made to add cresols phenolic resin varnish type epoxy resin EPICLON N-680, epoxide equivalent=215) 215 parts, and add 266.5 parts of carbitol acetates, and heating for dissolving.In this resin solution, add as 0.05 part of the quinhydrones of polymerization inhibitor with as 1.0 parts of the triphenylphosphines of catalysts.With this mixture heated to 85～95 ℃, slowly dropwise addition of acrylic acid is 72 parts, and makes its reaction 24 hours.Slowly dropping makes 208 parts of half urethanes that isophorone diisocyanate and pentaerythritol triacrylate obtain with 1: 1 molar reactive in advance in the epoxy acrylate of gained, and it was reacted 4 hours.The epoxy urethanes acrylate varnish that so has the compound (D) of two above ethylenically unsaturated groups in the molecule of processing gained is hereinafter referred to as D-1 varnish.
Use the resin solution of above-mentioned synthesis example 1～3, cooperate with the ratio (mass parts) shown in various compositions shown in the table 1 and the table 1, and after being pre-mixed with stirring machine, mixing with three roller mills, modulate each light solidifying/heat solidifying resin composition.Wherein, when the dispersion degree of each light solidifying/heat solidifying resin composition of gained is estimated with Erichsen corporate system hondrometer mensuration granularity, be below the 15 μ m.
Table 1
| Embodiment | Comparative example | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1 | 2 | |
| A-1 varnish | 154 | - | - | - | - | - | - | - | - | - | - | - |
| A-2 varnish | - | 154 | 154 | 154 | 154 | 154 | 154 | 154 | 154 | 154 | 154 | 154 |
| Photoepolymerizationinitiater initiater (B-1) *1 | 1 | 0.5 | 0.7 | 1 | 1 | 0.7 | 0.7 | 3 | 5 | 1 | 1 | - |
| Photoepolymerizationinitiater initiater (B-2) *2 | - | - | - | - | - | 0.3 | - | - | - | - | - | - |
| Photoepolymerizationinitiater initiater (B-3) *3 | - | - | - | - | - | - | 0.3 | - | - | - | - | - |
| Photoepolymerizationinitiater initiater (C-1) *4 | 6 | 3 | 6 | 6 | 6 | 6 | 6 | 6 | 10 | 6 | - | 15 |
| Photoepolymerizationinitiater initiater *5 | 1 | 1 | 1 | 1 | - | - | - | 1 | 1 | 1 | 1 | 1 |
| D-1 varnish | - | - | - | - | - | - | - | - | - | 20 | - | - |
| Compound (D-2) *6 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Compound (D-3) *7 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Filler (E-1) *8 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 |
| Thermocurable composition (F-1-1) *9 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Thermocurable composition (F-1-2) *10 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Phthalocyanine blue | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Yellow uitramarine *11 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 |
| The micro mist melamine | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| The silicone-based defoamer | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| DpM *12 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| #150 *13 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Remarks | *1:2-(acetoxyl group iminomethyl) thioxanthene-9-one *2:{1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1, the 2-acetyl caproyl, *3:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) ethyl ketone *4:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine aminoacetone-1 *The 5:2-isopropyl thioxanthone *6: dipentaerythritol acrylate *7: trimethylolpropane triacrylate *8: barium sulphate (the system B-30 of Sakai chemical industrial company) *9: phenol novolak type epoxy resin (Japanese chemical drug corporate system EPPN-201) *10: two diformazan phenol-type epoxy resins (Japan Epoxy Resin corporate system YX-4000) *11: anthraquinone is a yellow uitramarine *12: dipropylene glycol methyl ether acetate *13: fragrant family organic solvent (bright dipping petrochemistry corporate system trade name Ipsol#150) | |||||||||||
Performance evaluation:
＜deep curable 〉
After the circuit pattern substrate of line/be spaced apart 300/300, the thick 35 μ m of copper ground with polishing roll, after washing, the drying, by silk screen print method to its coating as the embodiment 1～10 of above-mentioned modulation and each light solidifying/heat solidifying resin composition of comparative example 1,2, and in 80 ℃ heated air circulation type drying oven dry 30 minutes.After the drying, use the direct drawing apparatus of the semiconductor laser that is equipped with maximum wavelength 350～370nm to expose.Exposing patterns is for using the pattern of spacer portion being described 20/30/40/50/60/70/80/90/100 μ m line.Exposure is with 40mJ/cm on photosensitive polymer combination
2The irradiation active energy beam.After the exposure, develop with 30 ℃ 1wt% aqueous sodium carbonates and to remove unexposed portion, thereby form pattern, then carry out 150 ℃ * 60 minutes heat curing and obtain cured coating film.
Use is adjusted to 200 times optical microscope with the minimum remaining line counting of the cured coating film of the light solidifying/heat solidifying resin composition of gained.In addition, cut off the line central portion, carry out mirror finish after, use footpath, top, footpath, bottom and the thickness of the minimum remaining line of the light microscope determining cured coating film that is adjusted to 1000 times.Metewand be footpath, the more little and bottom of minimum remaining line more near design load, then the deep curable is better.Its evaluation result is shown in table 2.
＜cross sectional shape 〉
After the circuit pattern substrate of line/be spaced apart 300/300, the thick 50 μ m of copper ground with polishing roll, after washing, the drying, be coated with each light solidifying/heat solidifying resin composition thereon by silk screen print method as above-mentioned embodiment 1～10 and comparative example 1,2, and in 80 ℃ heated air circulation type drying oven dry 30 minutes.After the drying, use the direct drawing apparatus of the semiconductor laser that is equipped with wavelength 350～370nm to expose.Exposing patterns is for using the pattern of spacer portion being described 20/30/40/50/60/70/80/90/100 μ m line.Exposure is for estimating the exposure of gained by above-mentioned optimum exposure.After the exposure, develop with the 1wt% aqueous sodium carbonate and to remove unexposed portion, form pattern, then carry out 1000mJ/cm with high-pressure sodium lamp
2Ultraviolet ray irradiation after, the heat curing of carrying out 150 ℃ * 60 minutes obtains cured coating film.Observe the xsect of the design load 100 μ m line portions of cured coating film.
As the synoptic diagram of Fig. 1 record, be divided into corresponding to 5 ranks of the A～E of Fig. 1 (A)～(E) this cross sectional shape is estimated.The synoptic diagram of Fig. 1 (A)～(E) when following phenomenon show to take place.Particularly in the situation that A estimates, the pattern coating film 2 that forms on the substrate 1 from live width design load L depart from online top, the bottom is in the 5 μ m.It the results are shown in table 2.
A estimates: as the such perfect condition (state shown in Fig. 1 (A)) of design width
B estimates: the live width on the online top that is taken place because of anti-development deficiency etc. reduces (state shown in Fig. 1 (B))
C estimates: undercutting state (state shown in Fig. 1 (C))
D estimates: because of the line chap (state shown in Fig. 1 (D)) of generation line bottoms such as halation
E estimates: the line chap and the undercutting (state shown in Fig. 1 (E)) on line top take place
＜surface cure 〉
After the circuit pattern substrate of line/be spaced apart 300/300, the thick 35 μ m of copper ground with polishing roll, after washing, the drying, by silk screen print method each light solidifying/heat solidifying resin composition to its coating previous embodiment 1～10 and comparative example 1,2, and in 80 ℃ heated air circulation type drying oven dry 60 minutes.After the drying, use the direct drawing apparatus of the semiconductor laser that is equipped with maximum wavelength 350～370nm to expose.Exposing patterns is for using whole exposing patterns.Exposure is with 40mJ/cm on photosensitive polymer combination
2The irradiation active energy beam.After the exposure, carry out developing for 60 seconds (30 ℃, spray press 0.2MPa, 1wt% aqueous sodium carbonate) remove unexposed portion, form pattern, then carry out 150 ℃ * 60 minutes heat curing and obtain cured coating film.
So handle the surface cure of the cured coating film that obtains and estimate 60 ° glossiness for using Grossmeters Microtrigross (manufacturing of BYK Gardner company).Metewand for be considered as more than 50 well with the glossiness after developing, glossiness less than 50 is considered as bad.Its evaluation result is shown in table 2.
＜thermal stability 〉
With above-mentioned＜surface cure〉evaluation method identical, on the copper circuit pattern substrate, form the cured coating film of each light solidifying/heat solidifying resin composition of previous embodiment 1～10 and comparative example 1,2, and use the optical microscope that is adjusted to 100 times to confirm that this cured coating film has or not and peel off.Metewand is for to be considered as well with situation about not peeling off, and no matter large or small and number needs only situation about peeling off and is considered as bad.Its evaluation result is shown in table 2.
＜absorbance 〉
In the mensuration of absorbance, use ultraviolet-visible pectrophotometer (Ubest-V-570DS that Japanese beam split Co., Ltd. makes) and integrating sphere device (ISN-470 that Japanese beam split Co., Ltd. makes).
After being applied to each light solidifying/heat solidifying resin composition of embodiment 1～10 and comparative example 1,2 on the glass plate with spreader, use the heated air circulation type drying oven in 80 ℃ of dryings 30 minutes, on glass plate, make the dry coating of light solidifying/heat solidifying resin composition.
Use ultraviolet-visible pectrophotometer and integrating sphere device, measure the absorbance baseline of 500～300nm with the glass plate identical with the glass plate that is coated with light solidifying/heat solidifying resin composition.On the other hand, measure the absorbance of the glass plate that has dry coating of made, and calculate the absorbance of dry coating itself, obtain the absorbance of target light wavelength 355nm according to above-mentioned baseline.For the absorbance skew that prevents that the coating film thickness skew from being caused, the coating thickness of spreader coating is divided the four-stage change and carries out this operation, make the chart of the absorbance that is coated with thick and 355nm, and calculate the absorbance of the dry coating of thickness 25 μ m by its approximate expression, be considered as absorbance separately.
Its evaluation result is shown in table 2.
Table 2
| Embodiment | Comparative example | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 1 | 2 | ||
| The deep curable | Minimum feature (μ m) | 80 | 70 | 50 | 50 | 60 | 60 | 30 | 50 | 70 | 40 | 90 | More than 100 |
| Cross sectional shape | A | D | A | A | D | A | A | C | E | A | B | - | |
| Surface cure | 60 ℃ of gloss | Well | Well | Well | Well | Well | Well | Well | Well | Well | Well | Bad | Well |
| Thermal stability | Peeling off on the circuit | Well | Well | Well | Well | Well | Well | Well | Well | Well | Well | Bad | Well |
| Absorbance | 355nm 25 μ m are thick | 0.65 | 0.38 | 0.52 | 0.68 | 0.43 | 0.54 | 0.64 | 1.17 | 1.55 | 0.6 | 0.46 | 1.10 |
Result shown in above-mentioned table 2 as can be known, light solidifying/heat solidifying resin composition of the present invention can be brought into play high photopolymerization ability to the laser of 350～370nm, and obtains sufficient deep curable, and surface cure and good heat stability.
In addition, making by the light solidifying/heat solidifying resin composition of embodiment 1～10, and embodiment 1～10 in remove the Photocurable resin composition that Thermocurable composition (F-1-1), (F-1-2) obtain, and solidify equally with the evaluation of surface cure, make and estimate substrate.After this is estimated substrate flooded for 10 seconds in 260 ℃ solder bath, carry out disbonded test with cellotape, acetonideexample 1～10 and no problem, but by removing the Photocurable resin composition that Thermocurable composition (F-1-1), (F-1-2) obtain among the embodiment 1～10, generation is expanded and is peeled off, and judges not have as the necessary thermotolerance of solder resist.
Embodiment 11～13 reaches than example 3～5
Use the resin solution of above-mentioned synthesis example 1～3, cooperate with the ratio (mass parts) shown in various compositions shown in the table 3 and the table 3, and after being pre-mixed with stirring machine, mixing with three roller mills, modulate each light solidifying/heat solidifying resin composition.Here, when the hondrometer that the dispersion degree of each light solidifying/heat solidifying resin composition of gained is made with Erichsen company is measured granularity and evaluation, be below the 15 μ m.
Table 3
| Embodiment | Comparative example | ||||||
| 11 | 12 | 13 | 3 | 4 | 5 | ||
| A-1 varnish | 154.0 | 30.0 | 30.0 | 154.0 | 30.0 | 30.0 | |
| A-2 varnish | - | 125.0 | 125.0 | - | 125.0 | 125.0 | |
| Photoepolymerizationinitiater initiater (B-1) *1 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | |
| Photoepolymerizationinitiater initiater (C-1) *2 | 12.0 | 12.0 | 12.0 | - | - | - | |
| Photoepolymerizationinitiater initiater *3 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
| D-1 varnish | - | - | 20.0 | - | - | 20.0 | |
| Compound (D-2) *4 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | |
| Compound (D-3) *5 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 | |
| Filler (E-1) *6 | 130.0 | 130.0 | 130.0 | 130.0 | 130.0 | 130.0 | |
| Thermocurable composition (F-1-1) *7 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | |
| Thermocurable composition (F-1-2) *8 | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | |
| Phthalocyanine blue | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| Yellow uitramarine *9 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | 0.75 | |
| The micro mist melamine | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | |
| The silicone-based defoamer | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | |
| DPM *10 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | |
| #150 *11 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | |
| Remarks | *1:2-(acetoxyl group iminomethyl) thioxanthene-9-one *2:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine amido acetone-1 *The 3:2-isopropyl thioxanthone *4: dipentaerythritol acrylate *5: trimethylolpropane triacrylate *6: barium sulphate (B-30 of Sakai chemical industrial company system) *7: phenol novolak type epoxy resin (EPPN-201 of Japanese chemical drug corporate system) *8: two diformazan phenol-type epoxy resins (Japan Epoxy Resin corporate system YX-4000) *9: chromium phthalocyanine Huang (Xiba Special Chemical Product Co.,Ltd's system) *10: dipropylene glycol methyl ether acetate *11: fragrant family organic solvent (bright dipping petrochemistry corporate system trade name Ipsol#150) | ||||||
Performance evaluation:
＜deep curable 〉
The direct drawing apparatus that is equipped with each semiconductor laser of maximum wavelength 355nm and 405nm as use except each light solidifying/heat solidifying resin composition of using embodiment 11～13 that operation like this modulates and comparative example 3～5 and exposure carries out, with aforementioned＜deep curable〉evaluation method handle the deep curable that evaluate cure is filmed.Its evaluation result is shown in table 4.
＜surface cure 〉
Except using each light solidifying/heat solidifying resin composition of previous embodiment 11～13 and comparative example 3～5, and exposure is beyond the direct drawing apparatus of each semiconductor laser of use lift-launch maximum wavelength 355nm and 405nm carries out, with aforementioned＜surface cure〉evaluation method handle the surface cure that evaluate cure is filmed.Its evaluation result is shown in table 4.
＜thermal stability 〉
Except each light solidifying/heat solidifying resin composition that uses previous embodiment 11～13 and comparative example 3～5, with aforementioned＜thermal stability〉evaluation method handle, estimate and have or not cured coating film to peel off.Its evaluation result is shown in table 4.
Table 4
| Embodiment | Comparative example | |||||||
| 11 | 12 | 13 | 3 | 4 | 5 | |||
| 355nm | Deep curable (μ m) | Minimum remaining wide | 50 | 50 | 40 | 70 | 70 | 60 |
| Top is wide | 51 | 51.5 | 40.5 | 71 | 72.5 | 62 | ||
| The bottom is wide | 52.5 | 51 | 41 | 66.5 | 65.5 | 55.5 | ||
| Thickness | 38.5 | 39 | 38 | 38.5 | 39 | 38.5 | ||
| Surface cure | 60 ° of gloss | Well | Well | Well | Bad | Bad | Well | |
| Thermal stability | That peels off has or not | Well | Well | Well | Bad | Bad | Bad | |
| 405nm | Deep curable (μ m) | Minimum remaining wide | 40 | 40 | 30 | 60 | 60 | 50 |
| Top is wide | 42 | 41 | 31.5 | 60.5 | 61 | 51 | ||
| The bottom is wide | 43.5 | 41 | 31 | 56 | 54 | 45 | ||
| Thickness | 38 | 38.5 | 38.5 | 38 | 39 | 39 | ||
| Surface cure | 60 ° of gloss | Well | Well | Well | Bad | Bad | Well | |
| Thermal stability | That peels off has or not | Well | Well | Well | Bad | Bad | Bad | |
Result shown in above-mentioned table 4 as can be known, light solidifying/heat solidifying resin composition of the present invention can be brought into play high photopolymerization ability to the laser of 350nm～420nm, and can obtain sufficient deep curable, and surface cure and good heat stability.
The direct drawing apparatus that is equipped with semiconductor laser is changed over the contact exposure machine (GW20 of ORC corporate system) that carries metal halide lamp, each light solidifying/heat solidifying resin composition of the foregoing description 11～13 is carried out same evaluating characteristics.
It the results are shown in table 5.
Table 5
| Embodiment | |||||
| 11 | 12 | 13 | |||
| Exposure with metal halide lamp | Deep curable (μ m) | Minimum remaining wide | 40 | 40 | 40 |
| Top is wide | 60 | 61 | 67 | ||
| The bottom is wide | 40 | 41 | 42 | ||
| Thickness | 38 | 38.5 | 38.5 | ||
| Surface cure | 60 ° of gloss | Well | Well | Well | |
| Thermal stability | That peels off has or not | Well | Well | Well | |
Result shown in above-mentioned table 5 as can be known, light solidifying/heat solidifying resin composition of the present invention, compare with the deep curable of table 4, top difference wide and that the bottom is wide is big under the situation of metal halide lamp, judges that light solidifying/heat solidifying resin composition of the present invention is the direct drawing apparatus that is suitable for laser.
Embodiment 14～21 and comparative example 6～8
Use the resin solution of above-mentioned synthesis example 1～3, cooperate with the ratio (mass parts) shown in various compositions shown in the table 6 and the table 6, and with after the stirring machine premixed, mixing with three roller mills, modulate each light solidifying/heat solidifying resin composition.Here, when the dispersion degree of each light solidifying/heat solidifying resin composition of gained is measured granularity and evaluation with Erichsen corporate system hondrometer, be below the 15 μ m.
Table 6
| Embodiment | Comparative example | |||||||||||
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 6 | 7 | 8 | ||
| A-1 varnish | 125 | 125 | 125 | - | 125 | 125 | 125 | 125 | 125 | 125 | 125 | |
| A-2 varnish | - | - | - | 154 | - | - | - | - | - | - | - | |
| Photoepolymerizationinitiater initiater (B-1) *1 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | - | - | 2 | |
| Photoepolymerizationinitiater initiater (C-2) *2 | - | 12 | 12 | 12 | 12 | 12 | 12 | 12 | - | 12 | - | |
| Photoepolymerizationinitiater initiater (C-2) *3 | 15 | 10 | 5 | 10 | 5 | 5 | 5 | 5 | 15 | 10 | - | |
| Photoepolymerizationinitiater initiater *4 | - | - | 0.6 | - | 0.6 | - | 0.6 | 0.6 | - | 0.6 | - | |
| Photoepolymerizationinitiater initiater *5 | - | - | - | - | 0.2 | 0.6 | 0.2 | 1.0 | - | 0.2 | - | |
| Phthalocyanine blue | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | |
| Yellow uitramarine *6 | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 | 0.7 | 2.3 | 2.3 | 2.3 | 2.3 | |
| D-1 varnish | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | |
| Compound (D-2) *7 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | |
| Compound (D-3) *8 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| Filler (E-1) *9 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | |
| Heat curing composition (F-1-1) *10 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | |
| Heat curing composition (F-1-2) *11 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| The micro mist melamine | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| The silicone-based defoamer | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| DPM *12 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| #150 *13 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Remarks | *1:2-(acetoxyl group iminomethyl) thioxanthene-9-one *2:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine amido acetone-1 *3:2,4,6-trimethylbenzoyl diphenyl phosphine oxide *4:2, the 4-diethyl thioxanthone *5:4,4 '-two diethylamino benzophenone *6: anthraquinone is a yellow uitramarine *7: dipentaerythritol acrylate *8: trimethylolpropane triacrylate *9: barium sulphate (the system B-30 of Sakai chemical industrial company) *10-phenol novolaks epoxy resin (Japanese chemical drug corporate system EPPN-201) *11: two diformazan phenol-type epoxy resins (Japan Epoxy Resin corporate system YX-4000) *12: dipropylene glycol methyl ether acetate *13: fragrant family organic solvent (bright dipping petrochemistry corporate system trade name Ipsol#150) | |||||||||||
Performance evaluation:
＜surface cure 〉
Except using each light solidifying/heat solidifying resin composition of previous embodiment 14～21 and comparative example 6～8, and exposure is for beyond the direct drawing apparatus that uses the royal purple laser be equipped with maximum wavelength 400～420nm carries out, with aforementioned＜surface cure〉evaluation method operate the surface cure that evaluate cure is filmed equally.Its evaluation result is shown in table 7.
＜cross sectional shape 〉
The direct drawing apparatus that is equipped with the royal purple laser of wavelength 405nm as use except each light solidifying/heat solidifying resin composition of using previous embodiment 14～21 and comparative example 6～8 and exposure carries out, with aforementioned＜cross sectional shape〉evaluation method operate the cross sectional shape that evaluate cure is filmed equally.Its evaluation result is shown in table 7.
＜thermal stability 〉
Except each light solidifying/heat solidifying resin composition that uses previous embodiment 14～21 and comparative example 6～8, with aforementioned＜thermal stability〉evaluation method handle, estimate and have or not peeling off of cured coating film.Its evaluation result is shown in table 7.
＜absorbance 〉
The mensuration of absorbance is used ultraviolet-visible pectrophotometer (Ubest-V-570DS that Japanese beam split Co., Ltd. makes), and integrating sphere device (ISN-470 that Japanese beam split Co., Ltd. makes).
After being applied to each light solidifying/heat solidifying resin composition of previous embodiment 14～21 and comparative example 6～8 on the glass plate with spreader, 80 ℃ were descended dry 30 minutes in the heated air circulation type drying oven, made the dry coating of light solidifying/heat solidifying resin composition on glass plate.
Use ultraviolet-visible pectrophotometer and integrating sphere device, measure the absorbance baseline of 500～300nm with the glass plate identical with the glass plate that is coated with light solidifying/heat solidifying resin composition.On the other hand, measure the absorbance of the glass plate that has dry coating of made, and calculate the absorbance of dry coating itself, obtain the absorbance of target light wavelength 405nm according to above-mentioned baseline.For the absorbance skew that prevents that the coating film thickness skew from being caused, the coating thickness of spreader coating is divided the four-stage change and carries out this operation, make the chart of the absorbance that is coated with thick and 405nm, and calculate the absorbance of the dry coating of thickness 25 μ m by its approximate expression, be considered as absorbance separately.
Its evaluation result is shown in table 7.
Table 7
| Embodiment | Comparative example | ||||||||||
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 6 | 7 | 8 | |
| Surface cure | △ | ○ | ○ | ○ | ○ | ○ | △ | ○ | × | × | △ |
| Cross sectional shape | A | A | A | A | A | A | D | C | B | C | E |
| Thermal stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × |
| 405nm absorbance (25 μ m are thick) | 0.64 | 0.66 | 0.77 | 0.67 | 0.83 | 0.84 | 0.40 | 1.26 | 0.56 | 0.75 | 0.61 |
Result shown in above-mentioned table 7 as can be known, light solidifying/heat solidifying resin composition of the present invention can be brought into play high photopolymerization ability to the laser of 400～420nm, and obtains sufficient deep curable, and then surface cure and good heat stability.
Utilizability on the industry
Light solidifying/heat solidifying resin composition of the present invention, it is good and be the laser generation light source of 350～420nm by wavelength that property is solidified in the deep, can form the pattern without halation, undercutting, can be used as laser and directly describe to use anticorrosive additive material, and can be used as the solder resist of printed circuit board (PCB) etc., the insulating resin layer of various electronic units.
Claims (15)
1. light solidifying/heat solidifying resin composition, it is characterized in that, said composition contains (A) carboxylic resin, (B) the oxime ester that contains the oxime ester base shown in the following general formula (I) is a Photoepolymerizationinitiater initiater, (C) aminoacetophenone with structure shown in the following general formula (II) is that Photoepolymerizationinitiater initiater (C-1) and/or the phosphine oxide that contains structure shown in the following general formula (III) are Photoepolymerizationinitiater initiater (C-2), (D) has the compound of two above ethylenically unsaturated groups in the molecule, (E) filling agent, reach (F) Thermocurable composition, and said composition can be developed by diluted alkaline solution, can be that the laser generation light source of 350nm～420nm solidifies by maximum wavelength.
(in the formula, R
1Be the alkyl or the phenyl of 1～7 of expression hydrogen atom, carbon number, R
2Be the alkyl or the phenyl of 1～7 of expression carbon number, R
3, R
4Be the alkyl or the aralkyl of 1～12 of expression carbon number, R
5, R
6Be the alkyl of 1～6 of expression hydrogen atom, carbon number, or R
5And R
6The ring-type alkane ether that the carbon number of be combined into is 4, R
7, R
8For the alkyl of the straight or branched of 1～6 of carbon number of expression, cyclohexyl, cyclopentyl, aryl, by aryl or any one acyl group that halogen atom, alkyl or alkoxy replaced for 1～20 of expression carbon number.)
2. light solidifying/heat solidifying resin composition, it is characterized in that, it is that aminoacetophenone that Photoepolymerizationinitiater initiater, (C-1) have a structure shown in the following general formula (II) is the compound that has 2 above ethylenically unsaturated groups in Photoepolymerizationinitiater initiater, (D) molecule, (E) filling agent, and (F) Thermocurable composition that said composition contains oxime ester that (A) carboxylic resin, (B) contain the oxime ester base shown in the following general formula (I), and said composition can be developed by diluted alkaline solution, can be that the laser generation light source of 350～370nm solidifies by maximum wavelength.
(in the formula, R
1Be the alkyl or the phenyl of 1～7 of expression hydrogen atom, carbon number, R
2Be the alkyl or the phenyl of 1～7 of expression carbon number, R
3, R
4Be the alkyl or the aralkyl of 1～12 of expression carbon number, R
5, R
6Alkyl or R for 1～6 of expression hydrogen atom, carbon number
5With R
6The ring-type alkane ether that the carbon number of be combined into is 4.)
3. light solidifying/heat solidifying resin composition according to claim 2, wherein, the dry coating of this light solidifying/heat solidifying resin composition is 0.3～1.5 when the absorbance of wavelength 355nm is thickness 25 μ m.
4. light solidifying/heat solidifying resin composition, it is characterized in that, it is that phosphine oxide that Photoepolymerizationinitiater initiater, (C-2) contain structure shown in the following general formula (III) is the compound that has 2 above ethylenically unsaturated groups in Photoepolymerizationinitiater initiater, (D) molecule, (E) filling agent, and (F) Thermocurable composition that said composition contains oxime ester that (A) carboxylic resin, (B) contain the oxime ester base shown in the following general formula (I), and said composition can be developed by diluted alkaline solution, can be that the laser generation light source of 400～420nm solidifies by maximum wavelength.
(in the formula, R
1Be the alkyl or the phenyl of 1～7 of expression hydrogen atom, carbon number, R
2Be the alkyl or the phenyl of 1～7 of expression carbon number, R
7, R
8For the alkyl of the straight chain shape of 1～6 of carbon number of expression or a chain, cyclohexyl, cyclopentyl, aryl, by aryl or any one acyl group that halogen atom, alkyl or alkoxy replaced for 1～20 of expression carbon number.)
5. light solidifying/heat solidifying resin composition according to claim 4, wherein, the dry coating of this light solidifying/heat solidifying resin composition is 0.3～1.5 when the absorbance of wavelength 405nm is thickness 25 μ m.
6. according to each described light solidifying/heat solidifying resin composition of claim 1～5, it is characterized in that, described carboxylic resin (A) contains the carboxyl photoresist for following acquisition: after making (a) polyfunctional epoxy resin and (b) unsaturated monocarboxylic reaction, make (c) multi-anhydride reaction obtain carboxylic resin, make the gained resin further with (d) molecule in have an oxirane ring and an above ethylenically unsaturated group the compound reaction obtain containing the carboxyl photoresist.
7. according to each described light solidifying/heat solidifying resin composition of claim 1～6, it is characterized in that the compound (D) that has two above ethylenically unsaturated groups in the described molecule is a resin for epoxy acrylate.
8. according to each described light solidifying/heat solidifying resin composition of claim 1～7, it is characterized in that described oxime ester is that Photoepolymerizationinitiater initiater (B) is the Photoepolymerizationinitiater initiater shown in the following formula (IV).
9. according to each described light solidifying/heat solidifying resin composition of claim 1～8, it is characterized in that further containing (G) thioxanthones is Photoepolymerizationinitiater initiater.
10. according to each described light solidifying/heat solidifying resin composition of claim 1～9, it is characterized in that, as the insulation course on the copper circuit.
11. the dry film of Photosetting and thermosetting, it is dry on carrier film and obtain with each the described light solidifying/heat solidifying resin composition coating of aforementioned claim 1～10.
12. solidfied material, it is each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or the described dry film of aforementioned claim 11, photocuring on copper and obtaining.
13. solidfied material, it obtains each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or the described dry film of aforementioned claim 11 with laser generation light source photocuring.
14. solidfied material, it is each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or the described dry film of aforementioned claim 11, with the wavelength is behind the laser photocuring of 350nm～420nm, heat curing obtains.
15. printed circuit board (PCB), it has solidfied material, this solidfied material is each described light solidifying/heat solidifying resin composition of aforementioned claim 1～10 or the described dry film of aforementioned claim 11, with the wavelength is behind the laser photocuring of 350nm～420nm, heat curing obtains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005160057 | 2005-05-31 | ||
| JP160057/2005 | 2005-05-31 | ||
| JP371215/2005 | 2005-12-26 | ||
| JP004687/2006 | 2006-01-12 | ||
| JP018327/2006 | 2006-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101189550A true CN101189550A (en) | 2008-05-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800192950A Pending CN101189550A (en) | 2005-05-31 | 2006-05-31 | Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101189550A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851411A (en) * | 2009-03-31 | 2010-10-06 | 太阳油墨制造株式会社 | Curable resin composition |
| CN104334604A (en) * | 2012-05-17 | 2015-02-04 | 太阳油墨制造株式会社 | Alkali-developable thermosetting resin composition, and printed wiring board |
-
2006
- 2006-05-31 CN CNA2006800192950A patent/CN101189550A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851411A (en) * | 2009-03-31 | 2010-10-06 | 太阳油墨制造株式会社 | Curable resin composition |
| CN101851411B (en) * | 2009-03-31 | 2012-08-08 | 太阳控股株式会社 | Curable resin composition |
| CN104334604A (en) * | 2012-05-17 | 2015-02-04 | 太阳油墨制造株式会社 | Alkali-developable thermosetting resin composition, and printed wiring board |
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Open date: 20080528 |