CN1296770C - Foam eliminating dispersing agent for developer solution of photosensitive resists - Google Patents
Foam eliminating dispersing agent for developer solution of photosensitive resists Download PDFInfo
- Publication number
- CN1296770C CN1296770C CNB2003101204686A CN200310120468A CN1296770C CN 1296770 C CN1296770 C CN 1296770C CN B2003101204686 A CNB2003101204686 A CN B2003101204686A CN 200310120468 A CN200310120468 A CN 200310120468A CN 1296770 C CN1296770 C CN 1296770C
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- developer solution
- resist
- acid
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Abstract
Provided is a defoaming dispersant for a resist developer solution, the dispersant having excellent defoaming property for foams in a developer solution and excellent dispersibility of scum produced in the developer solution in a developing process of a photoresist using the developer solution. The defoaming dispersant for a photoresist developer solution contains a partial fatty acid ester obtained by allowing a mixture fatty acid having the proportion of 5 to 300 parts by mass of 6-14C middle fatty acid with respect to 100 parts by mass of >=15C higher fatty acid to react with an aliphatic trihydric alcohol.
Description
Technical field
The present invention relates in the developing procedure of the photoresists (following only be called " resist ") that use developer solution the also good resist developer solution froth breaking spreading agent of dispersiveness of and the scum silica frost that in developer solution produce good for the defoaming of the foaming of developer solution.
Background technology
In the past, resist extensively was used in the formation of Wiring pattern of plated printed circuit, integrated circuit, color filter etc.In the formation operation of Wiring pattern, usually with membranaceous or liquid resist lamination or be applied on the base material, then to above-mentioned resist irradiation ultraviolet radiation, X ray, electron ray isoreactivity radioactive ray and exposure, after the sclerosis of resist pattern-like, by remove unhardened resist part (non-illuminated portion) with developer solution resist is developed, form the resist film of pattern-like.As developer solution, use alkaline aqueous solution usually, as the alkaline agent of developer solution, can use organic basic compounds such as inorganic alkaline compounds such as alkali carbonate, alkali metal hydroxide, tetramethyl ammonium hydroxide etc.
For this alkaline-based developer, dissolvings such as contained dyestuff, pigment, polymerization initiator, crosslinking chemical disperse, are blended in the developer solution in the resinous principle of the unhardened part of resist, the resist in the development of resist, their aggegations in developer solution, floating on developer solution surface or in developer solution, precipitate, in developer solution, generate so-called scum silica frost.This scum silica frost when developing attached to developing apparatus in, not only hinder the development of resist, and in a single day above-mentioned scum silica frost is attached to when developing and is developed on the thing resist or is provided with on the base material of resist, the resolution of resist will reduce, and existence can not form the problem of good resist pattern.Thereby, require developer solution to have and make the scum silica frost that in development, produces disperse and prevent the performance of scum silica frost aggegation.
On the other hand, when resist develops, when in developer solution, having air to enter, will foam in the developer solution, but owing to developer solution recycles usually, so in case the foam froth breaking that generates in the developer solution is insufficient, then foam will be put aside in developer solution.Recycling of developer solution particularly, along with dissolving in developer solution or the resist composition (resin etc.) that disperses increase, the foam that produces in the developer solution is difficult to eliminate.This foam not only hinders the good circulation of developer solution, and the contacting of obstruction and developer solution and resist, so cause the problem that can not fully remove unhardened resist part, can not form good resist pattern.In recent years, spray developing for the resist that becomes main flow, because by developing the resist after nozzle is ejected into developer solution exposure fully, be easy to cause foaming in developer solution, the inhibition of the foam in the developer solution has become very important problem with froth breaking.
In order to suppress the foaming of this developer solution, it is effective adding defoamer toward developer solution, but this defoamer aggegation in developer solution, become the scum silica frost of oily, when this scum silica frost is attached on resist or its substrate when developing, will exist not only to form good resist pattern, and be subjected to pollution problems by the substrate that resist forms.In general froth breaking purposes, silicon defoamer can improve defoaming effect, but silicon defoamer is easy to form the scum silica frost of oily, so defoamer of using as developer solution, for example can use acetylene alcohol surfactants (for example with reference to patent documentation 1), poly alkylene glycol or derivatives thereof (for example, with reference to patent documentation 2～7), higher fatty acid monoglyceride (for example, with reference to patent documentation 8) etc.
But, these defoamers in the past, dispersiveness to the scum silica frost that produces in developer solution can not be said so fully, this defoamer is at the initial stage of its use, though have defoaming effect to a certain degree, but along with the increase of the resist composition that dissolves in developer solution or disperse, defoaming effect sharply reduces, and also has the shortcoming that is easy to generate scum silica frost.
Patent documentation 1 special fair 4-51020 communique
Patent documentation 2 spies open flat 7-128865 communique
Patent documentation 3 spies open flat 8-10600 communique
Patent documentation 4 spies open flat 8-87382 communique
Patent documentation 5 spies open flat 9-172256 communique
Patent documentation 6 spies open flat 10-319606 communique
Patent documentation 7 spies open the 2001-222115 communique
Patent documentation 8 spies open flat 9-293964 communique
Summary of the invention
Therefore, the object of the present invention is to provide resist developer solution froth breaking spreading agent, this spreading agent is when the development of resist, even the resist composition of dissolving or dispersion increases in developer solution, when developer solution is had high defoaming, the dispersiveness of the scum silica frost that generates in developer solution is also good, can also prevent that scum silica frost is attached on resist or its substrate.
Therefore, the inventor just has the defoaming (following only be called sometimes " defoaming ") to developer solution and the reagent of the dispersiveness (following only be called sometimes " scum silica frost dispersiveness ") of the scum silica frost that produces in developer solution has been carried out diligent research, find to have the fatty acid mixed that specific fatty acid forms and the partial fatty acid ester of aliphatic tribasic alcohol and had good above-mentioned defoaming and scum silica frost dispersiveness, so far finished the present invention.Promptly, the present invention is the resist developer solution with froth breaking spreading agent (below be sometimes referred to as " partial fatty acid ester "), it is characterized in that containing with respect to carbon number 15 or 15 above higher fatty acid 100 mass parts, the ratio of the intermediate fatty acid of carbon number 6～14 is the fatty acid mixed of 5～300 mass parts and the partial fatty acid ester that the aliphatic tribasic alcohol reaction obtains, and contains the alkaline resist developer solution that above-mentioned foaming spreading agent is a feature.
Effect of the present invention is to provide resist developer solution froth breaking spreading agent, this spreading agent is when making resist develop with developer solution, even the resist composition of dissolving or dispersion increases in developer solution, when developer solution is had high defoaming, the dispersiveness of the scum silica frost that generates in developer solution is also good, can prevent that scum silica frost is attached on resist or its substrate.
Embodiment
In the present invention, so-called higher fatty acid is represented carbon number 15 or 15 above fatty acid, and so-called intermediate fatty acid is represented the fatty acid of carbon number 6～14.Raw material as partial fatty acid ester of the present invention is that fatty acid mixed is with respect to higher fatty acid 100 mass parts, and the ratio of intermediate fatty acid is the fatty acid mixed of 5～300 weight portions.The ratio of middle rank fatty acid is when being less than 5 mass parts, and resist developer solution of the present invention will reduce with the scum silica frost dispersiveness of froth breaking spreading agent, above in 300 mass parts, will reduce the defoaming of the foam that produces in developer solution.With respect to preferred 10～200 mass parts of ratio of the intermediate fatty acid of higher fatty acid 100 weight portions, more preferably 25～150 mass parts, most preferably 40～100 mass parts.
As carbon number 15 or 15 above higher fatty acid, can enumerate for example 15 carbonic acid, 16 carbonic acid (palmitic acid), 17 carbonic acid, 18 carbonic acid (stearic acid), 12-hydroxyl 18 carbonic acid (12-hydroxy stearic acid), 20 carbonic acid (arachidic acid), behenic acid (mountain Yu's acid), tetracosa carbon acid (carnaubic acid), 26 carbonic acid (cerinic acid), 28 carbonic acid linear saturated fatty acids such as (montanic acids); Branched chain fatty acids such as 2-amyl group n-nonanoic acid, 2-hexyldecanoic acid, 2-heptyl lauric acid, isostearic acid; Unsaturated fatty acids such as gaidic acid, oleic acid, vaccenic acid, elaidic acid, linoleic acid, leukotrienes, ricinoleic acid, cod acid, sinapic acid, shark acid etc.In these higher fatty acid, the fatty acid of preferred carbon number 16～22, more preferably 16～20 fatty acid, the most preferably fatty acid of carbon number 16～18.
As the intermediate fatty acid of carbon number 6～14, can enumerate for example caproic acid (caproic acid), enanthic acid, sad (inferior caprylic acid), n-nonanoic acid (pelargonic acid), capric acid (caprylic acid), hendecoic acid, lauric acid (lauric acid), ficocerylic acid, ten tetra-carbonics linear saturated fatty acids such as (myristic acids); Branched chain fatty acids such as isocaproic acid, isoamyl acetic acid, 2 ethyl hexanoic acid, isooctyl acid, different n-nonanoic acid, 2-propylheptanoic acid, isodecyl acid, different hendecoic acid, sad, the different lauric acid of 2-butyl, different ficocerylic acid; Unsaturated fatty acids such as undecenoic acid.In these in the level fatty acid, the fatty acid of preferred carbon number 7～14, the more preferably fatty acid of carbon number 8～13, the most preferably fatty acid of carbon number 10～12.
In addition, the raw material of partial fatty acid ester of the present invention is that fatty acid mixed is the fatty acid mixed of only being made up of linear saturated fatty acids with it, the fatty acid mixed that does not contain linear saturated fatty acids and branched chain fatty acid or straight chain unsaturated fatty acid in this way, scum silica frost dispersiveness in the developer solution that is brought by partial fatty acid ester of the present invention becomes good,, thereby be preferred simultaneously because this partial fatty acid ester is easy to disperse in developer solution.The ratio of branched chain fatty acid in the fatty acid mixed and straight chain unsaturated fatty acid is with respect to the fatty acid mixed total amount, preferred 5～80 quality %, more preferably 10～70 quality %, most preferably 15～60 quality %.
In addition, the raw material of partial fatty acid ester of the present invention is a fatty acid mixed so long as the scope that is subjected to baneful influence in the defoaming or the scum silica frost dispersiveness that do not make resist developer solution of the present invention with the froth breaking spreading agent, also can contain the carboxylic acid beyond aforementioned intermediate fatty acid and the higher fatty acid.
As the aliphatic tribasic alcohol of the raw material of partial fatty acid ester of the present invention, can enumerate glycerine, 1,2,3-butantriol, 1,2,4-butantriol, 2-methylol-1, ammediol, 2-methyl isophthalic acid, 2,3-glycerine, 1,2,5-penta triol, 1,3,5-penta triol, 2-methyl isophthalic acid, 2,4-glycerine, 2-methylol-1,3-butylene glycol, trimethylolethane, 1,3,5-hexanetriol, 1,2,6-hexanetriol, 3-methylol-1,5-pentanediol, 3-methyl isophthalic acid, 3,5-penta triol, trimethylolpropane, tri hydroxy methyl butane, 2,5-dimethyl-1,2,5-hexanetriol etc.In these aliphatic triols, from the dispersed aspect of scum silica frost, the aliphatic triol of preferred carbon number 3～6, more preferably glycerine, 1,3,5-penta triol, trimethylolethane, 1,2,6-hexanetriol and trimethylolpropane, more preferably glycerine, trimethylolethane and trimethylolpropane, most preferably glycerine.
The partial fatty acid ester that aforementioned fatty acid mixed esterification is obtained with aliphatic tribasic alcohol is the potpourri of mono fatty acid ester (hereinafter referred to as " monoesters "), di fatty acid ester (hereinafter referred to as " diester ") and tri-fatty acid ester (hereinafter referred to as " three esters ") normally.In partial fatty acid ester of the present invention, in the too many occasion of the content of three esters, because aforementioned scum silica frost dispersiveness reduces sometimes, so with respect to the partial fatty acid ester total amount, the content of preferred three esters is below the 20 quality %, is more preferably below the 10 quality %, most preferably is below the 5 quality %.In addition, because in the too many occasion of the content of diester, defoaming to developer solution reduces, in occasion very little, the scum silica frost dispersiveness reduces sometimes, thus the ratio of monoesters in the partial fatty acid ester of the present invention and diester with respect to monoesters 100 weight portions, preferred diester is 5～1500 mass parts, being more preferably 10～500 mass parts, most preferably is 20～150 mass parts.
Partial fatty acid ester of the present invention can be made with known method.As known method, for example can enumerate the method etc. of the ester exchange reaction of three esters such as ester exchange reaction method, (c) fatty acid glyceride of the low-carbon-ester of direct esterification method, (b) fatty acid mixed of (a) fatty acid mixed and aliphatic tribasic alcohol and aliphatic tribasic alcohol and aliphatic tribasic alcohol.In addition, reaction as required, also can be made with extra care the partial fatty acid ester of generation after finishing.For example, can make with extra care, obtain monoesters or the high partial fatty acid ester of two ester contents by molecular distillation etc.
For resist developer solution froth breaking spreading agent of the present invention, further the polyether polyols ester of the higher fatty acid by containing carbon number 10～20 improves scum silica frost dispersiveness and defoaming.This polyether polyols ester by carbon number 10～20 fatty acid and the reaction of the oxyalkylene addition product of polyvalent alcohol or polyhydric phenol obtain.
As aforementioned polyvalent alcohol, except that aforementioned aliphatic tribasic alcohol, can enumerate for example ethylene glycol, propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, neopentyl glycol, isoamyl glycol (3-methyl isophthalic acid, 3-butylene glycol), 1, dibasic alcohol such as 6-hexanediol; Other trihydroxy alcohol such as triethanolamine, triisopropanolamine; Pentaerythrite, diglycol, D-sorbite, N, N, N ', tetra-atomic alcohols such as N '-four (2-hydroxypropyl) ethylenediamine; The alcohol that quaternarys such as methyl glucoside, dipentaerythritol, sucrose are above etc.
As aforementioned polyhydric phenol, can enumerate for example dihydric phenols such as bisphenol-A, Bisphenol F, catechol, quinhydrones; Trihydric phenols such as three (4-hydroxy phenyl) methane, three (4-hydroxy phenyl) ethane etc.
In these polyvalent alcohols and polyhydric phenol, preferred dibasic alcohol, more preferably ethylene glycol, propylene glycol and 1,2-butylene glycol, most preferably propylene glycol.
As with the oxyalkylene of polyvalent alcohol or polyhydric phenol addition, can enumerate for example ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1, the 4-epoxy butane), long-chain alpha-olefin oxide, styrene oxide etc.The addition mode can be random copolymers, segmented copolymer or the random/segmented copolymer etc. of homopolymer, the oxyalkylene more than 2 kinds of a kind of oxyalkylene etc.Particularly preferably be the copolymerization of ethylene oxide and propylene oxide, at this moment, with respect to 100 mass parts propylene oxides, the ratio of preferred ethylene oxide is 5～100 mass parts, more preferably 10～60 mass parts, most preferably 15～40 mass parts.This is that the scum silica frost dispersiveness in the developer solution becomes insufficient sometimes because the ratio of ethylene oxide is lower than 5 mass parts, if surpass 100 mass parts, then the foamability of developer solution increases.
The addition molal quantity of the oxyalkylene of the oxyalkylene addition product of aforementioned polyvalent alcohol or polyhydric phenol is preferred 20～200, and more preferably 30～150, most preferably 40～120.
In addition, in the fatty acid of aforementioned carbon number more than 10～20, viewpoint from the dispersiveness of scum silica frost, the fatty acid of preferred carbon number 10～16, more preferably 10～14 fatty acid, preferred especially 10～14 linear saturated fatty acids, viewpoint from defoaming, the fatty acid of preferred carbon number 14～20, the more preferably fatty acid of carbon number 16～18, the most preferably linear saturated fatty acids in the saturated fatty acid of carbon number 16～18.
In the scope of not damaging its performance, resist developer solution of the present invention also can contain other composition with the froth breaking spreading agent.As this composition, can enumerate water-soluble solvents such as ethanol, ethylene glycol, propylene glycol, dipropylene glycol, glycerine, butylene glycol, hexanediol; The oxyalkylene addition product of monohydroxy alcohol or monohydric phenol or its fatty acid ester, colorant etc.
Using resist developer solution of the present invention is alkaline-based developer with the developer solution of froth breaking spreading agent.As the alkaline agent of developer solution, can enumerate for example alkali carbonates such as lithium carbonate, sodium carbonate, sal tartari; Alkali metal hydrogencarbonates such as lithium bicarbonate, sodium bicarbonate, saleratus; Alkali borates such as lithium borate, sodium borate, potassium borate; Alkali silicates such as lithium metasilicate, sodium silicate, potassium silicate; Inorganic alkaline compounds such as alkali metal hydroxide such as lithium hydroxide, NaOH, potassium hydroxide; Organic basic compounds such as ethylenediamine, propane diamine, pyrrolidine, morpholine, piperazine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide trimethyl (2-hydroxyethyl) ammonium etc.In these alkaline agents, preferred alkali metal carbonate and organic basic compound, more preferably sodium carbonate and tetramethyl ammonium hydroxide.
The concentration of the alkaline agent in the developer solution is different because of the kind of the suitable resist of kind, the developer solution of the alkaline agent of use, in the occasion of alkali carbonate, with respect to 100 mass parts water, preferably 0.1～5 mass parts, more preferably 0.3～3 mass parts, most preferably 0.5～2 mass parts.In addition, in the occasion of organic basic compound, the concentration of the alkaline agent in the developer solution is with respect to 100 mass parts water, 0.5～25 mass parts preferably, and more preferably 1～15 mass parts most preferably is 1.5～10 mass parts.
Preferred 15～50 ℃ of the temperature of the developer solution when using above-mentioned developer solution that resist is developed, more preferably 20～40 ℃, most preferably 25～35 ℃.This be because, the temperature of developer solution is than 15 ℃ of low occasions, becomes insufficient during being dissolved with of unhardened resist part, and surpasses 50 ℃ occasion, the resist of sclerosis is partly sometimes from strippable substrate.
In addition, in the scope of not damaging purpose of the present invention, also can in resist developer solution of the present invention, suitably add the adding ingredient that in the past used with routine in the developer solution, for example can suitably add various known surfactants, lubricant, stabilizing agent, dissolution aids etc. at resist.
There is no particular limitation with the use amount of froth breaking spreading agent to resist developer solution of the present invention, can select use amounts according to the various conditions such as kind of the concentration of the kind of developer solution, developer solution, developing method, resist.For example in of dry film (membranaceous resist) development of 1 quality % aqueous sodium carbonate as developer solution, for developer solution, convert with the pure composition of glycerine partial fatty acid ester, preferably use 0.005～0.2 quality % resist developer solution froth breaking spreading agent of the present invention.In addition, adding method both can directly add partial fatty acid ester, also can add behind the dilute with water partial fatty acid ester again.Perhaps, also can add the partial fatty acid ester of partial fatty acid ester or dilute with water during developer solution, and add in the developer solution of foaming also passable in preparation.Partial fatty acid ester of the present invention both may be used alone, can also be two or more kinds in combination.
In addition, no matter the resist that becomes the development object of developer solution of the present invention is minus, eurymeric, so long as can develop with alkaline aqueous solution, whatsoever the resist of sample all can utilize.For example can enumerate (1) particularly and contain the eurymeric resist of naphthoquinones two triazo-compounds and phenolics; (2) contain by the acidic compound that exposes, decompose, the compound that the dissolubility of alkaline aqueous solution is increased and the eurymeric resist of alkali soluble resin with acid; (3) contain by the acidic compound that exposes, decompose, have the eurymeric resist of the alkali soluble resin of the group that the dissolubility to alkaline aqueous solution increases with acid; (4) contain negative resist by the acidic compound that exposes, crosslinking chemical, alkali soluble resin; (5) contain by exposure and produce compound, the crosslinking chemical of free radical, the negative resist of alkali soluble resin; (6) contain by exposure produce free radical compound, have the negative resist etc. of the alkali soluble resin of free-radical polymerised group.
Embodiment
Be described more specifically the present invention with comparative example by the following examples.In addition, if not otherwise specified, " part " in following embodiment and the comparative example and " % " expression quality.
In test, use the embodiment 1～9 shown in following and the defoamer of comparative example 1～10.Embodiment 1～7 and comparative example the 1, the 2nd with the partial fatty acid ester of aliphatic tribasic alcohol with the fatty acid mixed esterification, are displayed in Table 1 out this fatty acid and form (%) and ester composition (%).In addition, fatty acid is formed according to benchmark grease analytic approach, after the sample saponification, carries out esterification, with gas chromatography (detecting device: FID) measure.In addition, ester is formed with TLC-FID method (ヤ ト ロ Application company, model イ ア ト ロ ス キ ヤ Application MK5) mensuration.
Table 1
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | ||
| Aliphatic tribasic alcohol | G | G | G | G | G | TP | TP | G | G | |
| Fatty acid is formed (%) | Sad | 2 | - | 2 | 5 | - | 2 | - | - | - |
| Different n-nonanoic acid | - | 30 | - | 5 | - | - | 30 | - | - | |
| Capric acid | 2 | - | 2 | 10 | 6 | 2 | - | - | 1 | |
| Lauric acid | 10 | - | 10 | - | - | 10 | 10 | - | 98 | |
| Ten tetra-carbonics | 38 | 3 | 24 | - | - | 38 | - | - | 1 | |
| 16 carbonic acid | 4 | 19 | 2 | 1 | 3 | 4 | 24 | 39 | - | |
| 18 carbonic acid | 4 | 13 | 28 | 8 | 11 | 4 | 36 | 61 | - | |
| Palmitoleic acid | - | - | - | 2 | 2 | - | - | - | - | |
| Oleic acid | 34 | 2 | 30 | 68 | 77 | 34 | - | - | - | |
| Linoleic acid | 6 | 3 | 2 | 1 | 1 | 6 | - | - | - | |
| Leukotrienes | - | 30 | - | - | - | - | - | - | - | |
| Intermediate acid amounts to | 52 | 33 | 38 | 20 | 6 | 52 | 40 | 0 | 100 | |
| Higher acid amounts to | 48 | 67 | 62 | 80 | 94 | 48 | 60 | 100 | 0 | |
| The branched acids unsaturated acid amounts to | 40 | 65 | 32 | 76 | 80 | 40 | 30 | 0 | 0 | |
| Ester is formed (%) | Monoesters | 42 | 16 | 69 | 43 | 79 | 65 | 95 | 45 | 98 |
| Diester | 50 | 83 | 22 | 55 | 17 | 31 | 5 | 51 | 2 | |
| Three esters | 8 | 1 | 9 | 2 | 4 | 4 | 0 | 4 | 0 | |
In the table, G represents glycerine, and TP represents trimethylolpropane
Embodiment 8
The potpourri that 100 parts of the partial fatty acid esters of embodiment 1 and polyether polyols ester (two ten caprylates of the block addition product that 80 moles of propylene oxides of propylene glycol and ethylene oxide are 30 moles) are 50 parts.
Embodiment 9
The potpourri that 100 parts of the partial fatty acid esters of embodiment 2 and polyether polyols ester (trilaurin of the random addition product that 50 moles of propylene oxides of trimethylolpropane and ethylene oxide are 30 moles) are 50 parts.
Comparative example 3
2,4,7,9-tetramethyl ten-5-alkynes-4,10 moles of addition products of the ethylene oxide of 7-glycol.
Comparative example 4
Polypropylene glycol (number-average molecular weight 700).
Comparative example 5
Polyoxypropylene glycerine ether (number-average molecular weight 1000).
Comparative example 6
18 carbonic acid (stearic acid) ester of the block addition product that 40 moles of propylene oxides of 18 alcohol (stearyl alcohol) and ethylene oxide are 8 moles.
Comparative example 7
2,2-diethyl-1, the block addition product that 20 moles of propylene oxides of ammediol and ethylene oxide are 20 moles.
Comparative example 8
Ten caprylates of the block addition product of comparative example 7.
Comparative example 9
Two ten caprylates of the block addition product that 80 moles of propylene oxides of propylene glycol and ethylene oxide are 30 moles.
Comparative example 10
The laurate of the random addition product that 50 moles of propylene oxides of trimethylolpropane and ethylene oxide are 30 moles.
The preparation of＜experimental liquid 〉
Toward 1% sodium carbonate (Na
2CO
3) 100 parts of aqueous solution add 0.05 part of each defoamer of embodiment 1～9 and comparative example 1～10, make developer solution.To be dissolved in by the dry film that unexposed acrylic compounds photoresist is made in this developer solution so that the concentration of this resin reaches 0.2g/L, it as experimental liquid, will be used in the following test.In addition, also can replace 1% aqueous sodium carbonate, carry out same test with 2.5% tetramethyl ammonium hydroxide (TMAH) aqueous solution.
＜defoaming test 〉
Graduated cylinder toward the band ground stopper of capacity 100mL adds above-mentioned experimental liquid 50mL, leaves standstill after the vibration in 1 minute 50 times, observes the state of bubble, with following benchmark evaluation defoaming.
Zero: 15 second does not arrive, lather collapse, and defoaming is good.
△: at 15～60 seconds, lather collapse, defoaming is bad slightly.
*: even surpass 60 seconds, foam does not disappear yet, and defoaming is bad.
＜scum silica frost dispersivity test 1 〉
In 400mL glass container with a lid, add afore-mentioned test liquid 300mL, be placed on 30 ℃ 1 week of dark place, with visual judgement sediment amount, with following benchmark evaluation scum silica frost dispersiveness.
◎: do not see sediment, the scum silica frost favorable dispersibility.
Zero: see sediment slightly, the scum silica frost dispersiveness is good slightly.
△: see the small amount of precipitate thing, the scum silica frost dispersiveness is bad slightly.
*: see a large amount of sediments, the scum silica frost dispersiveness is bad.
＜scum silica frost dispersivity test 2 〉
The dry film lamination that to be made by the acrylic compounds photoresist is on printed base plate, after partly exposing with mercury vapor lamp, with afore-mentioned test liquid processing (30 ℃ of the liquid temperature of spraying, spray time 10 seconds, atomisation pressure 150kPa), by visual judgement scum silica frost to the adhering to of dry film or substrate, with following benchmark evaluation scum silica frost dispersiveness.
◎: do not see adhering to of scum silica frost, the scum silica frost favorable dispersibility.
Zero: see adhering to of scum silica frost a little, the scum silica frost dispersiveness is good slightly.
△: see that a small amount of scum silica frost adheres to, the scum silica frost dispersiveness is bad slightly.
*: see that a large amount of scum silica frost adhere to, the scum silica frost dispersiveness is bad.
Table 2
| The defoamer of experimental liquid | Na 2CO 3The class experimental liquid | The TMAH experimental liquid | |||||
| Defoaming | Dispersed 1 | Dispersed 2 | Defoaming | Dispersed 1 | Dispersed 2 | ||
| Embodiment | 1 | ○ | ◎ | ◎ | ○ | ◎ | ◎ |
| 2 | ○ | ○ | ○ | ○ | ○ | ○ | |
| 3 | ○ | ◎ | ◎ | ○ | ◎ | ◎ | |
| 4 | ○ | ◎ | ◎ | ○ | ◎ | ◎ | |
| 5 | ○ | ◎ | ○ | ○ | ○ | ◎ | |
| 6 | ○ | ◎ | ○ | ○ | ○ | ○ | |
| 7 | ○ | ○ | ◎ | ○ | ◎ | ○ | |
| 8 | ○ | ◎ | ◎ | ○ | ◎ | ◎ | |
| 9 | ○ | ◎ | ○ | ○ | ○ | ◎ | |
| Comparative example | 1 | ○ | × | × | △ | × | × |
| 2 | × | ○ | △ | × | △ | ○ | |
| 3 | × | △ | △ | △ | △ | × | |
| 4 | △ | × | × | × | × | △ | |
| 5 | △ | × | × | △ | × | × | |
| 6 | △ | × | × | △ | △ | × | |
| 7 | × | △ | × | × | × | × | |
| 8 | △ | × | △ | △ | × | △ | |
| 9 | △ | × | × | △ | × | × | |
| 10 | × | △ | × | × | × | × | |
Industrial utilizability
According to the present invention, when resist development, even the resist composition of dissolving or dispersion increases in developer solution, in the high defoaming that has developer solution, the dispersiveness of the scum silica frost that produces in developer solution is also good, can provide to prevent that scum silica frost is attached to the resist development liquid froth breaking dispersant on resist or its substrate.
Claims (8)
1. photoresists developer solution froth breaking spreading agent, it is characterized in that, contain: the ratio with respect to the intermediate fatty acid of carbon number 15 or 15 above higher fatty acid 100 mass parts, carbon number 6～14 is the fatty acid mixed of 5～300 mass parts and the partial fatty acid ester that the aliphatic tribasic alcohol reaction generates; Wherein partial fatty acid ester is the potpourri of mono fatty acid ester, di fatty acid ester and tri-fatty acid ester.
2. the described photoresists developer solution froth breaking spreading agent of claim 1, wherein, in partial fatty acid ester, with respect to mono fatty acid ester 100 mass parts, the ratio of di fatty acid ester is 10～500 mass parts; With respect to the partial fatty acid ester total amount, the content of tri-fatty acid ester is below the 10 quality %.
3. the described photoresists developer solution froth breaking spreading agent of claim 1, wherein, the content of branched chain fatty acid in the fatty acid mixed and straight chain unsaturated fatty acid is 5～80 quality % with respect to the fatty acid mixed total amount.
4. the described photoresists developer solution froth breaking spreading agent of claim 2, wherein, the content of branched chain fatty acid in the fatty acid mixed and straight chain unsaturated fatty acid is 5～80 quality % with respect to the fatty acid mixed total amount.
5. each described photoresists developer solution froth breaking spreading agent of claim 1～4, wherein, aliphatic tribasic alcohol is the aliphatic tribasic alcohol of carbon number 3～6.
6. each described photoresists developer solution froth breaking spreading agent of claim 1～4 wherein further contains the polyether polyols ester of the fatty acid of carbon number 10～20.
7. the described photoresists developer solution froth breaking spreading agent of claim 5 wherein further contains the polyether polyols ester of the fatty acid of carbon number 10～20.
8. an alkaline photoresists developer solution is characterized in that, contains each described photoresists developer solution froth breaking spreading agent of claim 1～5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP316395/02 | 2002-10-30 | ||
| JP2002316395 | 2002-10-30 | ||
| JP316395/2002 | 2002-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1503057A CN1503057A (en) | 2004-06-09 |
| CN1296770C true CN1296770C (en) | 2007-01-24 |
Family
ID=34260193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101204686A Expired - Fee Related CN1296770C (en) | 2002-10-30 | 2003-10-30 | Foam eliminating dispersing agent for developer solution of photosensitive resists |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100719208B1 (en) |
| CN (1) | CN1296770C (en) |
| TW (1) | TW200406253A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100573316C (en) * | 2005-07-08 | 2009-12-23 | 上海纺印印刷包装有限公司 | A kind of convex-pattern type thermosensitive/photosensitive plate developing liquid and preparation method thereof |
| CN101721945B (en) * | 2009-11-09 | 2012-01-11 | 健雄职业技术学院 | High-performance defoamer |
| CN102466986A (en) * | 2010-11-09 | 2012-05-23 | 苏州瑞红电子化学品有限公司 | Anticorrosion alkaline developing composition |
| EP2677365B1 (en) * | 2011-02-16 | 2019-01-23 | Toyobo Co., Ltd. | Developer composition for printing plate, developer and method for manufacturing printing plate |
| CN111965958A (en) * | 2020-09-07 | 2020-11-20 | 苏州理硕科技有限公司 | Developing solution for dry film photoresist and preparation method thereof |
| CN117298664B (en) * | 2023-11-27 | 2024-01-23 | 山东尚正新材料科技股份有限公司 | Polyether polyol ester defoamer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0810600A (en) * | 1994-06-30 | 1996-01-16 | Toho Chem Ind Co Ltd | Defoaming and dispersing agent for photosensitive resin |
| JPH09293964A (en) * | 1996-04-26 | 1997-11-11 | Matsushita Electric Works Ltd | Manufacture of lamination board with inner layer circuit |
| CN1188506A (en) * | 1995-06-23 | 1998-07-22 | 花王株式会社 | Defoamer for fermentation and process for fermentative production with use of the same |
| CN1228111A (en) * | 1996-06-26 | 1999-09-08 | 普罗格特-甘布尔公司 | Low sudsing liquid detergent compositions comprising silicone suds suppressor and fatty acid ester |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3656174B2 (en) * | 1996-02-29 | 2005-06-08 | サンノプコ株式会社 | Antifoam composition |
| JP3238078B2 (en) | 1996-10-03 | 2001-12-10 | 伯東株式会社 | Antifoam composition |
| JP3690773B2 (en) | 1998-03-26 | 2005-08-31 | サンノプコ株式会社 | Oil-in-water emulsion defoamer composition |
| DE19903546A1 (en) | 1999-01-29 | 2000-08-03 | Basf Ag | Defoamers and / or deaerators based on oil-in-water dispersions |
-
2003
- 2003-10-22 TW TW092129216A patent/TW200406253A/en not_active IP Right Cessation
- 2003-10-29 KR KR1020030075752A patent/KR100719208B1/en not_active IP Right Cessation
- 2003-10-30 CN CNB2003101204686A patent/CN1296770C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0810600A (en) * | 1994-06-30 | 1996-01-16 | Toho Chem Ind Co Ltd | Defoaming and dispersing agent for photosensitive resin |
| CN1188506A (en) * | 1995-06-23 | 1998-07-22 | 花王株式会社 | Defoamer for fermentation and process for fermentative production with use of the same |
| JPH09293964A (en) * | 1996-04-26 | 1997-11-11 | Matsushita Electric Works Ltd | Manufacture of lamination board with inner layer circuit |
| CN1228111A (en) * | 1996-06-26 | 1999-09-08 | 普罗格特-甘布尔公司 | Low sudsing liquid detergent compositions comprising silicone suds suppressor and fatty acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200406253A (en) | 2004-05-01 |
| TWI332860B (en) | 2010-11-11 |
| KR100719208B1 (en) | 2007-05-16 |
| KR20040038767A (en) | 2004-05-08 |
| CN1503057A (en) | 2004-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5037359B2 (en) | Cleaning liquid for photolithography and exposure apparatus cleaning method using the same | |
| CN1194267C (en) | Diluent composition for removing unnecessary sensitive resin | |
| TW201720881A (en) | Lithographic printing ink, varnish for lithographic inks, and method for producing printed matter using said ink | |
| CN1717632A (en) | Rinse liquid for lithography and method for forming resist pattern using same | |
| US20050176605A1 (en) | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture | |
| CN1277157C (en) | Method for forming fine resist pattern | |
| CN1296770C (en) | Foam eliminating dispersing agent for developer solution of photosensitive resists | |
| JP6899220B2 (en) | Composition for removing resist | |
| CN1751275A (en) | Water soluble resin composition, method of pattern formation and method of inspecting resist pattern | |
| CN1716093A (en) | Photo-corrosion-resisting agent composition and rubbing method, organic layer pattern manufacture method, LCD without spin | |
| CN101133366A (en) | Developer composition, process for producing the same, and method of forming resist pattern | |
| CN1811602A (en) | Developer solution composition | |
| CN1424626A (en) | Forming method for photoresist design and its laminating products | |
| JP2013506041A (en) | Defoamer for airless paint spray application | |
| JP2006016438A (en) | Electronic part-washing liquid | |
| WO2007052544A1 (en) | Washing liquid and washing method | |
| WO1991000763A1 (en) | Low viscosity defoaming/antifoaming formulations | |
| CN1930525A (en) | Stable high pH developer | |
| KR101161051B1 (en) | Developer composition | |
| CN1271470C (en) | Foam-removing agent composition for photoresist solution | |
| JP2004170928A (en) | Defoaming dispersant for photoresist developer solutions | |
| KR101073417B1 (en) | Photoresist composition | |
| CN1670628A (en) | Resist composition | |
| CN100557514C (en) | A kind of photoresistance developer solution | |
| TWI417651B (en) | Resist composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1063347 Country of ref document: HK |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1063347 Country of ref document: HK |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070124 Termination date: 20111030 |