TWI734816B - Detergent composition for screen plate - Google Patents

Detergent composition for screen plate Download PDF

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Publication number
TWI734816B
TWI734816B TW106125434A TW106125434A TWI734816B TW I734816 B TWI734816 B TW I734816B TW 106125434 A TW106125434 A TW 106125434A TW 106125434 A TW106125434 A TW 106125434A TW I734816 B TWI734816 B TW I734816B
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detergent composition
component
screen
group
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TW106125434A
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Chinese (zh)
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TW201819615A (en
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何政輝
川下浩一
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日商花王股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5086—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being different from alcohols, e.g. mixtures of water and ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

本發明提供一種洗淨性及脫液性優異之網版用洗淨劑組合物。 本發明於一態樣中係關於一種網版用洗淨劑組合物，其含有相對於25℃之水100 g之溶解度未達10 g之胺(成分A)或其鹽、相對於25℃之水100 g之溶解度為0.02 g以上且未達10 g之溶劑(成分B)、及水，且上述成分A係選自碳數為6以上且26以下之一級胺、二級胺及三級胺之至少1種。The present invention provides a detergent composition for a screen plate with excellent detergency and liquid releasability. In one aspect, the present invention relates to a detergent composition for a screen plate, which contains an amine (component A) or a salt thereof with a solubility of less than 10 g relative to 100 g of water at 25°C, and a salt relative to 25°C. Solvents (component B) with a solubility of 0.02 g or more and less than 10 g in 100 g of water, and water, and the above component A is selected from the group consisting of primary amines, secondary amines and tertiary amines with a carbon number of 6 or more and 26 or less At least one of them.

Description

網版用洗淨劑組合物Detergent composition for screen

本發明係關於一種網版用洗淨劑組合物及網版之洗淨方法。The present invention relates to a detergent composition for a screen plate and a method for cleaning the screen plate.

於將電子零件安裝於印刷基板或陶瓷基板等時，一般進行焊接。通常於焊接時，為了去除焊料及母材表面之氧化膜、或者防止焊料及母材表面之再氧化從而獲得充分之焊料連接，而使用助焊劑。然而，助焊劑由於為腐蝕性且助焊劑殘渣會使印刷配線基板之品質降低，故而提出有各種用以將助焊劑殘渣洗淨去除之洗淨劑組合物。 例如，於專利文獻1中揭示有一種工業用洗淨劑組合物，其用於洗淨助焊劑殘渣或金屬加工油等各種污染物，包含特定之水溶性二醇醚75～94.99重量%、具有170～270℃之沸點之有機胺類0.01～5重量%、及水5～20重量%，且實質上不含其他成分。 於專利文獻2中揭示有一種洗淨劑組合物，其用於洗淨於印刷基板製造時之任意步驟中殘留在基板上之助焊劑及再熔解液，且包含二醇系溶劑、胺類及/或界面活性劑。 近年來，就低耗電、高速處理等觀點而言，電子零件不斷小型化，伴隨於此，配線圖案正進行微細化。為了形成微細之配線，主要進行使用網版之網版印刷。然而，因網版之反覆使用造成之助焊劑或焊料膏等各種膏於網版表面之附著會導致配線不良等製品不良，擔憂今後成為較大之問題。然而，先前之洗淨劑組合物對於附著於網版之助焊劑或焊料膏等污染物之洗淨性並不充分。進而，限制氟氯碳化物以前起使用之洗淨裝置仍被大量使用，雖然洗淨劑經脫氟氯碳化物化，但於洗淨裝置之構成及構造上而言，洗淨後不進行沖洗而直接乾燥後使用網版，因此，為了獲得較高之生產性，對洗淨劑要求快速乾燥性或脫液性。進而，於使用如具有易燃性之有機溶劑之情形時，必須設置嚴格之設備而設為防爆規格，要求不具有易燃性、即含有高沸點且低揮發性之水並且具有快速乾燥性、脫液性及能夠應對微細配線之高洗淨性的洗淨劑。 例如，於專利文獻3中揭示有一種金屬遮罩用洗淨劑，其含有：具有一定之沸點且為水溶性之1種或2種以上之二醇醚系化合物25～45重量%、具有一定之沸點與一定量之水溶性之1種或2種以上之二醇醚系化合物5～25重量%、胺系化合物0.005～1.0重量%及水(剩餘量)。 於專利文獻4中揭示有一種洗淨劑，其係用以洗淨附著有有機EL材料之被洗淨物者，且係含有包含二丙二醇丙醚之類之特定丙二醇5～80質量%及N-甲基-2-吡咯啶酮之類之特定吡咯啶酮類20～95質量%的組合物而成。 於專利文獻5中揭示有一種網版洗淨用組合物，其含有低沸點之親水性二醇醚單烷基醚、高沸點之親水性二醇醚單烷基醚及水。 先前技術文獻 專利文獻 專利文獻1：日本專利特開平9-87668號公報 專利文獻2：日本專利特開平5-125395號公報 專利文獻3：日本專利特開平9-59688號公報 專利文獻4：日本專利特開2006-265300號公報 專利文獻5：日本專利特開2000-267293號公報When mounting electronic components on a printed circuit board or ceramic substrate, etc., soldering is generally performed. Generally, during soldering, in order to remove the oxide film on the surface of the solder and the base material, or to prevent the re-oxidation of the surface of the solder and the base material, so as to obtain a sufficient solder connection, a flux is used. However, since the flux is corrosive and the flux residue will degrade the quality of the printed wiring board, various detergent compositions for cleaning and removing the flux residue have been proposed. For example, Patent Document 1 discloses an industrial detergent composition for cleaning various contaminants such as flux residues and metalworking oils, and contains 75 to 94.99% by weight of specific water-soluble glycol ethers and has Organic amines with a boiling point of 170 to 270°C are 0.01 to 5% by weight, and water is 5 to 20% by weight, and substantially no other ingredients. Patent Document 2 discloses a detergent composition, which is used to clean the flux and remelting liquid remaining on the substrate in any step during the production of the printed circuit board, and contains a glycol-based solvent, amines, and / Or surfactant. In recent years, from the viewpoints of low power consumption and high-speed processing, electronic components have been miniaturized, and with this, wiring patterns have been miniaturized. In order to form fine wiring, screen printing using a screen is mainly performed. However, the adhesion of various pastes such as flux or solder paste on the surface of the screen caused by repeated use of the screen may cause defective wiring and other product defects, which is worrying that it will become a major problem in the future. However, the previous detergent composition is not sufficiently cleansable for contaminants such as flux or solder paste adhering to the screen. Furthermore, the cleaning devices that have been used since the restriction of chlorofluorocarbons are still being used in large quantities. Although the cleaning agent has been de-chlorofluorocarbonized, in terms of the structure and structure of the cleaning device, the cleaning device is not rinsed after cleaning. The screen is used directly after drying. Therefore, in order to obtain higher productivity, the detergent requires rapid drying or deliquation. Furthermore, when using flammable organic solvents, strict equipment must be installed and set to explosion-proof specifications. It is required to be non-flammable, that is, to contain water with high boiling point and low volatility and have fast drying properties. Detergent with high detergency and ability to cope with fine wiring. For example, Patent Document 3 discloses a cleaning agent for metal masks, which contains: 25 to 45% by weight of one or two or more glycol ether compounds having a certain boiling point and being water-soluble. The boiling point and a certain amount of water-soluble one or two or more glycol ether compounds 5-25% by weight, amine compounds 0.005-1.0% by weight, and water (the remaining amount). Patent Document 4 discloses a detergent, which is used to clean the object to be cleaned with organic EL material attached, and contains 5 to 80% by mass of specific propylene glycol such as dipropylene glycol propyl ether and N -Methyl-2-pyrrolidone and other specific pyrrolidones such as 20 to 95% by mass composition. Patent Document 5 discloses a screen-cleaning composition which contains a low-boiling hydrophilic glycol ether monoalkyl ether, a high-boiling hydrophilic glycol ether monoalkyl ether, and water. Prior Art Document Patent Document Patent Document 1: Japanese Patent Laid-Open No. 9-87668 Patent Document 2: Japanese Patent Laid-Open No. 5-125395 Patent Document 3: Japanese Patent Laid-Open No. 9-59688 Patent Document 4: Japanese Patent Japanese Patent Application Publication No. 2006-265300 Patent Document 5: Japanese Patent Application Publication No. 2000-267293

[發明所欲解決之問題] 隨著網版之配線圖案之微細化，為了防止因網版之反覆使用造成之助焊劑或焊料膏等各種膏於網版表面之殘留所導致之製品缺陷，對洗淨劑要求更高之洗淨性。進而，為了獲得較高之生產性，較佳為於洗淨後能夠快速乾燥，對洗淨劑要求快速脫液性。然而，上述專利文獻中記載之方法無法同時實現高洗淨性與快速脫液性。 因此，本發明提供一種洗淨性及脫液性優異之網版用洗淨劑組合物及洗淨方法。 [解決問題之技術手段] 本發明於一態樣中係關於一種網版用洗淨劑組合物，其含有相對於25℃之水100 g之溶解度未達10 g之胺(成分A)或其鹽、相對於25℃之水100 g之溶解度為0.02 g以上且未達10 g之溶劑(成分B)、及水，且上述成分A係選自碳數為6以上且26以下之一級胺、二級胺及三級胺之至少1種。 本發明於一態樣中係關於一種網版之洗淨方法，其包含使用本發明之洗淨劑組合物洗淨被洗淨物之步驟，且上述被洗淨物為網版印刷後之網版。 本發明於一態樣中係關於一種本發明之洗淨劑組合物之用途，其用於洗淨網版印刷後之網版。 本發明於一態樣中係關於一種本發明之洗淨劑組合物之用途，其用於將助焊劑及焊料膏之至少一者自網版去除。 [發明之效果] 根據本發明，可提供一種洗淨性及脫液性優異之網版用洗淨劑組合物。並且，藉由使用本發明之洗淨劑組合物，可縮短網版之洗淨及乾燥所耗費之時間，效率良好地獲得潔淨度優異之網版，進而，可提高高品質之印刷基板或陶瓷基板等電子零件之生產效率。[Problem to be solved by the invention] With the miniaturization of the wiring pattern of the screen, in order to prevent product defects caused by the residue of various pastes such as flux or solder paste on the surface of the screen caused by the repeated use of the screen, Detergents require higher detergency. Furthermore, in order to obtain higher productivity, it is preferable to be able to dry quickly after washing, and rapid deliquoring properties are required for the detergent. However, the method described in the above-mentioned patent documents cannot achieve both high detergency and rapid deliquoring properties at the same time. Therefore, the present invention provides a cleaning composition and cleaning method for a screen plate having excellent cleaning properties and deliquoring properties. [Technical Means to Solve the Problem] In one aspect, the present invention relates to a detergent composition for a screen plate, which contains an amine (component A) whose solubility is less than 10 g with respect to 100 g of water at 25° C. Salt, a solvent (component B) with a solubility of 0.02 g or more and less than 10 g with respect to 100 g of water at 25°C (component B), and water, and the above component A is selected from a grade amine with a carbon number of 6 or more and 26 or less, At least one of secondary amine and tertiary amine. In one aspect, the present invention relates to a method for cleaning a screen plate, which includes the step of using the detergent composition of the present invention to clean an object to be cleaned, and the object to be cleaned is a screen after screen printing. Version. The present invention in one aspect relates to the use of the detergent composition of the present invention, which is used to clean the screen after screen printing. In one aspect, the present invention relates to a use of the detergent composition of the present invention, which is used to remove at least one of flux and solder paste from a screen. [Effects of the Invention] According to the present invention, it is possible to provide a cleaning composition for a screen plate having excellent cleaning properties and deliquoring properties. In addition, by using the detergent composition of the present invention, the time spent in cleaning and drying the screen can be shortened, and a screen with excellent cleanliness can be obtained efficiently, and further, high-quality printed substrates or ceramics can be improved The production efficiency of electronic components such as substrates.

本發明係基於如下知識見解：藉由在用於洗淨網版之洗淨劑組合物中含有相對於25℃之水100 g之溶解度未達10 g且碳數為6～26之一～三級胺(成分A)、及相對於25℃之水100 g之溶解度為0.02 g以上且未達10 g之溶劑(成分B)，可提高洗淨性，且脫液性變快。 即，本發明於一態樣中係關於一種網版用洗淨劑組合物(以下亦稱為「本發明之洗淨劑組合物」)，其含有相對於25℃之水100 g之溶解度未達10 g之胺(成分A)或其鹽、相對於25℃之水100 g之溶解度為0.02 g以上且未達10 g之溶劑(成分B)、及水，且上述成分A係選自碳數為6以上且26以下之一級胺、二級胺及三級胺之至少1種。根據本發明，可提供一種洗淨性及脫液性優異之網版用洗淨劑組合物。並且，藉由使用本發明之洗淨劑組合物，可縮短網版之洗淨及乾燥所耗費之時間，效率良好地獲得潔淨度優異之網版，進而，可提高高品質之印刷基板或陶瓷基板等電子零件之生產效率。 本發明之洗淨劑組合物之效果之詳細作用機制雖有不明確之部分，但推測如下。 若將本發明之洗淨劑組合物用於洗淨網版印刷後之網版，則洗淨劑組合物中之成分A之胺於水中之溶解度較低，具有低親水性即疏水性，因此吸附於網版表面，而使網版表面疏水化。並且，成分A於網版表面疏水化之同時會向助焊劑等油性成分吸附或滲透，使油性成分之流動性提高，而與網版表面電荷排斥。認為藉由如上所述成分A作用於網版表面與助焊劑等油性成分，可將油性成分自網版剝離(去除)，進而防止去除之油性成分再次附著於網版。再者，認為於利用洗淨劑組合物進行洗淨時，利用由噴霧或超音波產生之物理力之輔助而容易將油性成分自網版去除。推測由於如上所述能夠自網版去除油性成分並防止再次附著，進而可抑制油性成分之凝集，因此洗淨性提高。並且，推測由於網版表面疏水化及/或洗淨劑組合物之表面張力較大，故而脫液性變快。 又，推測洗淨劑組合物中之成分B之溶劑由於對水具有某程度之溶解度，故而與成分A相溶，可使成分A於水中均勻地穩定化並容易向助焊劑等油性成分吸附或滲透，因此洗淨性提高。 進而推測，於成分A與酸形成鹽之情形、尤其於本發明之洗淨劑組合物中進而調配酸(成分C)而使成分A之胺與成分C之酸形成鹽之情形時，藉由於洗淨劑組合物中存在胺與酸之鹽，向助焊劑等油性成分之滲透性提高，能夠於更短之時間內表現上述效果。 但是，本發明亦可不限定於該機制地加以解釋。 [成分A：胺] 本發明之洗淨劑組合物含有相對於25℃之水100 g之溶解度未達10 g之胺(成分A)或其鹽。於本發明中，成分A可使用1種或混合2種以上使用。 成分A之相對於25℃之水100 g之溶解度未達10 g，就洗淨性及脫液性之觀點而言，較佳為8 g以下，更佳為5 g以下，進而較佳為2 g以下，進而更佳為1 g以下，進而更佳為0.5 g以下，進而更佳為0.2 g以下，進而更佳為0.1 g以下，並且，就同樣之觀點而言，較佳為0.0001 g以上，更佳為0.001 g以上，進而較佳為0.01 g以上。 就洗淨性及脫液性之觀點而言，成分A之胺係選自碳數為6以上且26以下之一級胺、二級胺及三級胺之至少1種。成分A之碳數就洗淨性及脫液性之觀點而言，為6以上，較佳為7以上，更佳為8以上，並且，就同樣之觀點而言，為26以下，較佳為18以下，更佳為12以下，進而較佳為10以下。於成分A為鹽之形態之情形時，作為用以形成鹽之抗衡離子，並無特別限定，例如可列舉成分C之酸。 作為成分A，就洗淨性及脫液性之觀點而言，較佳為選自式(I)所表示之化合物之至少1種。 [化1]

Figure 02_image001
式(I)中，R1 表示選自碳數5以上且18以下之直鏈或支鏈烷基、及碳數5以上且18以下之直鏈或支鏈烯基之至少1種，R2 及R3 相同或不同，表示選自碳數1以上且5以下之直鏈或支鏈烷基及氫原子之至少1種，且R1 、R2 及R3 之碳數之合計為6以上且26以下。 式(I)中，R1 之碳數就洗淨性及脫液性之觀點而言，為5以上，較佳為6以上，更佳為7以上，並且，就抑制起泡(以下亦稱為「抑泡性」)之觀點而言，為18以下，較佳為12以下，更佳為10以下，進而較佳為8以下。 式(I)中，就洗淨性及脫液性之觀點而言，R2 及R3 分別獨立為選自碳數1以上且5以下之直鏈或支鏈烷基及氫原子之至少1種，較佳為選自碳數1或2之直鏈烷基及氫原子之至少1種，更佳為甲基或氫原子，進而較佳為氫原子。 式(I)中，R1 、R2 及R3 之合計碳數就洗淨性及脫液性之觀點而言，為6以上，較佳為7以上，更佳為8以上，並且，就抑泡性之觀點而言，為26以下，較佳為18以下，更佳為12以下，進而較佳為10以下。 作為成分A之鹽，就洗淨性及脫液性之觀點而言，可列舉選自上述式(I)所表示之化合物之至少1種化合物與酸之鹽。作為酸，只要為與成分A形成水溶性鹽者，則並無特別限定，例如可列舉下述成分C之酸。 本發明之洗淨劑組合物於洗淨時之成分A之含量就洗淨性及脫液性之觀點而言，較佳為0.001質量%以上，更佳為0.01質量%以上，進而較佳為0.02質量%以上，並且，就洗淨性、脫液性及抑泡性之觀點而言，較佳為2.0質量%以下，更佳為1.0質量%以下，進而較佳為0.7質量%以下，進而更佳為0.2質量%以下，進而更佳為0.15質量%以下，進而更佳為0.1質量%以下。於成分A為2種以上之胺之組合之情形時，成分A之含量係指其等之合計含量。 於本發明中，「洗淨劑組合物於洗淨時之各成分之含量」於一個或複數個實施形態中，係指用於洗淨步驟之洗淨劑組合物之各成分之含量。 [成分B：溶劑] 本發明之洗淨劑組合物含有相對於25℃之水100 g之溶解度為0.02 g以上且未達10 g之溶劑(成分B)。於本發明中，成分B可使用1種或混合2種以上使用。 成分B之相對於25℃水之溶解度就洗淨性及脫液性之觀點而言，為0.02 g以上，較佳為0.05 g以上，更佳為0.1 g以上，進而較佳為0.2 g以上，並且，就同樣之觀點而言，未達10 g，較佳為5 g以下，更佳為3g以下，進而較佳為2 g以下。 作為成分B，就洗淨性及脫液性之觀點而言，可列舉具有上述範圍內之溶解度之除成分A以外之溶劑，例如可列舉具有上述範圍內之溶解度且選自二醇醚系溶劑及醇系溶劑之至少1種。作為上述二醇醚系溶劑，就洗淨性及脫液性之觀點而言，較佳為選自下述式(II)所表示之化合物之至少1種。 R4 O-(EO)m (PO)n -H (II) 上述式(II)中，R4 表示碳數3以上且12以下之烴基，EO表示環氧乙烷基，m為EO之加成莫耳數且為0以上且5以下之數，PO表示環氧丙烷基，n為PO之加成莫耳數且為0以上且2以下之數，m＋n≧1，EO與PO之加成形態可為嵌段亦可為無規，且EO與PO之加成順序不受限定。 式(II)中，就提高洗淨性及脫液性之觀點而言，R4 為碳數3以上且12以下之烴基，較佳為碳數6以上且10以下之烴基，更佳為碳數6以上且8以下之烴基。 式(II)中，(EO)m (PO)n 可由環氧乙烷基單獨構成，亦可由環氧乙烷基與環氧丙烷基構成。於(EO)m (PO)n 係由環氧乙烷基與環氧丙烷基構成之情形時，EO與PO之排列可為無規亦可為嵌段。於EO與PO之排列為嵌段之情形時，EO之嵌段數、PO之嵌段數只要各平均加成莫耳數為上述範圍內，則分別可為1個亦可為1個以上。於包含EO之嵌段之數為2個以上之情形時，各嵌段中之EO之重複數可相互相同亦可不同。 作為成分B之具體例，例如可列舉：選自乙二醇單2-乙基己基醚(溶解度：0.20 g)、二乙二醇單2-乙基己基醚(溶解度：0.20 g)、乙二醇單己醚(溶解度：1.00 g)、二乙二醇單己醚(溶解度：1.40 g)、丙二醇單苯醚(苯氧基丙醇，溶解度：0.20 g)、二丙二醇單丙醚(溶解度：5.60 g)、丙二醇單丁醚(溶解度：6.60 g)之1種或2種以上之組合。就提高脫液性之觀點而言，較佳為選自乙二醇單2-乙基己基醚(溶解度：0.20 g)、乙二醇單己醚(溶解度：1.00 g)、二乙二醇單己醚(溶解度：1.40 g)及丙二醇單苯醚(溶解度：0.20 g)之1種或2種以上之組合，更佳為選自乙二醇單2-乙基己基醚(溶解度：0.20 g)、二乙二醇單己醚(溶解度：1.40 g)及丙二醇單苯醚(溶解度：0.20 g)之1種或2種以上之組合，進而較佳為乙二醇單2-乙基己基醚(溶解度：0.20 g)及二乙二醇單己醚(溶解度：1.40 g)之任一者，進而更佳為乙二醇單2-乙基己基醚(溶解度：0.20 g)。括弧內之溶解度表示相對於25℃之水100 g之溶解度。 本發明之洗淨劑組合物於洗淨時之成分B之含量就洗淨性及脫液性之觀點而言，較佳為0.1質量%以上，更佳為0.5質量%以上，進而較佳為1質量%以上，進而更佳為2質量%以上，並且，就同樣之觀點而言，較佳為20質量%以下，更佳為15質量%以下，進而較佳為12質量%以下，進而更佳為10質量%以下。於成分B為2種以上之溶劑之組合之情形時，成分B之含量係指其等之合計含量。 本發明之洗淨劑組合物中成分A之含量相對於成分B之含量的比A/B就洗淨性及脫液性之觀點而言，較佳為0.001以上，更佳為0.002以上，進而較佳為0.003以上，並且，就同樣之觀點而言，較佳為0.1以下，更佳為0.09以下，進而較佳為0.08以下。 [成分C：酸] 本發明之洗淨劑組合物可進而含有酸(成分C)。又，本發明之洗淨劑組合物可設為進而調配有酸(成分C)者。於本發明中，成分C可使用1種或混合2種以上使用。 作為成分C，就洗淨性及脫液性之觀點而言，較佳為與成分A形成鹽之酸，更佳為選自如下化合物及甲酸之1種或2種以上之酸，上述化合物具有1～3個選自羧基、磺酸基、硫酸基及磷酸基之至少1種基，且碳數為2以上且12以下。 作為成分C之具體例，例如可列舉：選自甲酸、乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、2-乙基己酸、壬酸、癸酸、月桂酸、草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、乙醇酸、乳酸、羥基丙二酸、羥基丁酸、甘油酸、蘋果酸、酒石酸、檸檬酸、甲磺酸、苯磺酸、對甲苯磺酸、萘磺酸、月桂基硫酸酯、2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)及二伸乙基三胺五(亞甲基膦酸)之1種或2種以上之組合，就洗淨性及脫液性之觀點而言，更佳為選自甲酸、乙酸、辛酸、2-乙基己酸、乳酸、檸檬酸、對甲苯磺酸及1-羥基亞乙基-1,1-二膦酸之1種或2種以上之組合，進而較佳為選自甲酸、乙酸、2-乙基己酸、檸檬酸、對甲苯磺酸及1-羥基亞乙基-1,1-二膦酸之1種或2種以上之組合，進而更佳為選自甲酸、乙酸、對甲苯磺酸及1-羥基亞乙基-1,1-二膦酸之1種或2種以上之組合，進而更佳為乙酸及對甲苯磺酸之任一者，進而更佳為乙酸。 本發明之洗淨劑組合物於洗淨時之成分C之含量(或調配量)就洗淨性及脫液性之觀點而言，較佳為0.001質量%以上，更佳為0.005質量%以上，進而較佳為0.01質量%以上，並且，就洗淨性、脫液性及將起泡抑制為較低之觀點而言，較佳為2.0質量%以下，更佳為1.0質量%以下，進而較佳為0.7質量%以下，進而更佳為0.2質量%以下，進而更佳為0.15質量%以下，進而更佳為0.1質量%以下。於成分C為2種以上之酸之組合之情形時，成分C之含量(或調配量)係指其等之合計含量(或合計調配量)。 本發明之洗淨劑組合物中成分A之含量相對於成分C之含量(或調配量)的比A/C就洗淨性及脫液性之觀點而言，較佳為0.1以上，更佳為0.2以上，進而較佳為0.4以上，並且，就同樣之觀點而言，較佳為10以下，更佳為7以下，進而較佳為5以下。 [成分D：水] 本發明之洗淨劑組合物含有水(成分D)。作為成分D之水，可使用離子交換水、RO(Reverse Osmosis，逆滲透)水、蒸餾水、純水、超純水。水之含量只要根據本發明之洗淨劑組合物之使用態樣進行適當設定即可。 本發明之洗淨劑組合物於洗淨時之成分D之含量就洗淨性之觀點而言，較佳為70質量%以上，更佳為80質量%以上，進而較佳為85質量%以上，並且，就同樣之觀點而言，較佳為99質量%以下，更佳為97質量%以下，進而較佳為95質量%以下。 [任意成分] 本發明之洗淨劑組合物於無損本發明之效果之範圍內，可除上述成分A～D以外視需要含有任意成分。作為任意成分，例如可列舉：選自非離子性界面活性劑；羥基乙基胺基乙酸、羥基乙基亞胺基二乙酸、乙二胺四乙酸等胺基羧酸鹽等具有螯合力之化合物；防腐劑；防銹劑；殺菌劑；抗菌劑；聚矽氧等消泡劑；抗氧化劑；椰油脂肪酸甲酯、乙酸苄酯等酯；烴系溶劑；醇類等之1種或2種以上之組合。 本發明之洗淨劑組合物於洗淨時之任意成分之含量就不阻礙本發明之效果之觀點而言，較佳為0質量%以上且2.0質量%以下，更佳為0質量%以上且1.5質量%以下，進而較佳為0質量%以上且1.3質量%以下，進而更佳為0質量%以上且1.0質量%以下。於本發明之洗淨劑組合物含有2種以上之任意成分之情形時，任意成分之含量係指其等之合計含量。 [洗淨劑組合物之pH值] 本發明之洗淨劑組合物於洗淨時之pH值就洗淨性及脫液性之觀點而言，較佳為12以下，更佳為9以下，進而較佳為8以下，進而更佳為7以下，並且，就洗淨性、脫液性及防止洗淨設備之腐蝕之觀點而言，較佳為4以上，更佳為4.5以上，進而較佳為5以上，進而更佳為5.5以上。於本發明中，「洗淨時之pH值」係指於25℃下使用洗淨劑組合物時(稀釋後)之pH值，可使用pH值計進行測定。具體可藉由實施例中記載之方法進行測定。 本發明之洗淨劑組合物之pH值調整例如可使用硝酸、硫酸等無機酸；羥基羧酸、多元羧酸、胺基聚羧酸、胺基酸等有機酸；及其等之金屬鹽或銨鹽、氨、氫氧化鈉、氫氧化鉀、胺等鹼性物質等進行。 [洗淨劑組合物之製造方法] 本發明之洗淨劑組合物可藉由將上述成分A、成分B及成分D、以及視需要之成分C及任意成分利用公知之方法進行調配而製造。例如，本發明之洗淨劑組合物可設為至少調配上述成分A、成分B及成分D而成者。因此，本發明於一態樣中係關於一種洗淨劑組合物之製造方法，其包含至少將上述成分A、成分B及成分D進行調配之步驟。於本發明中，所謂「調配」，包括將成分A、成分B及成分D、以及視需要之成分C及任意成分同時混合或按任意順序進行混合。於本發明之洗淨劑組合物之製造方法中，各成分之調配量可設為與上述本發明之洗淨劑組合物之各成分之含量相同。 本發明之洗淨劑組合物就儲存及運輸之觀點而言，亦可製備為減少成分D之水量而得之濃縮物。洗淨劑組合物之濃縮物就儲存及運輸之觀點而言，較佳為製成稀釋倍率3倍以上之濃縮物，就保管穩定性之觀點而言，較佳為製成稀釋倍率200倍以下之濃縮物。洗淨劑組合物之濃縮物能夠於使用時以各成分之含量成為上述含量(即，洗淨時之含量)之方式利用水稀釋而使用。進而，洗淨劑組合物之濃縮物亦能夠於使用時分別添加各成分而使用。於本發明中，洗淨劑組合物之濃縮物之「使用時」或「洗淨時」係指洗淨劑組合物之濃縮物被稀釋之狀態。 [被洗淨物] 本發明之洗淨劑組合物於一個或複數個實施形態中可用於洗淨網版印刷後之網版、及洗淨附著有助焊劑、焊料膏、銀膏、銅膏等導電膏等之網版。作為網版，例如可列舉金屬遮罩、樹脂遮罩、電鑄遮罩、乳劑遮罩等。 因此，本發明於一態樣中係關於一種本發明之洗淨劑組合物之用途，其用於洗淨網版印刷後之網版。進而，本發明於另一態樣中係關於一種本發明之洗淨劑組合物之用途，其用於將助焊劑及焊料膏之至少一者自網版去除。 [洗淨方法] 本發明於一態樣中係關於一種網版之洗淨方法(以下亦稱為「本發明之洗淨方法」)，其包含使用本發明之洗淨劑組合物洗淨被洗淨物之步驟(以下亦稱為「洗淨步驟」)。於本發明之洗淨劑組合物為濃縮物之情形時，本發明之洗淨方法可進而包含將洗淨劑組合物之濃縮物稀釋之步驟。作為被洗淨物，可列舉上述被洗淨物。上述洗淨步驟於一個或複數個實施形態中，可包括使本發明之洗淨劑組合物與被洗淨物接觸。作為使用本發明之洗淨劑組合物洗淨被洗淨物之方法，例如可列舉：將被洗淨物浸漬於洗淨槽中而使洗淨劑組合物與被洗淨物接觸之方法、於超音波洗淨裝置之浴槽內使洗淨劑組合物與被洗淨物接觸之方法、使洗淨劑組合物噴霧狀射出而與被洗淨物接觸之方法等。 本發明之洗淨方法可進而包含不沖洗上述洗淨後之網版而進行乾燥之步驟。藉此，可縮短網版之洗淨及乾燥所耗費之時間，效率良好地獲得潔淨度優異之網版，可提高高品質之印刷基板或陶瓷基板等電子零件之生產性。 本發明之洗淨方法就容易發揮本發明之洗淨劑組合物之洗淨力之方面而言，較佳為於本發明之洗淨劑組合物與被洗淨物之接觸時照射超音波。作為超音波之照射條件，例如可設定為20～2000 kHz。 [套組] 本發明於一態樣中係關於一種套組(以下亦稱為「本發明之套組」)，其係用於製造本發明之洗淨劑組合物者，且其於不使構成本發明之洗淨劑組合物之上述成分A、上述成分B及上述成分D中之至少1種成分與其他成分混合之狀態下保管。根據本發明，可提供一種能夠獲得洗淨性及脫液性優異之洗淨劑組合物之套組。 作為本發明之套組，例如可列舉如下套組(2液型洗淨劑組合物)，其係於不使含有成分B之溶液(第1液)與含有成分A、C及D之1種或2種以上之溶液(第2液)相互混合之狀態下保存，且於使用時將該等進行混合。上述第1液及第2液之各者中亦可視需要混合有上述任意成分。 本發明進而係關於以下之洗淨劑組合物、洗淨方法、製造方法及套組。 ＜1＞一種網版用洗淨劑組合物，其含有相對於25℃之水100 g之溶解度未達10 g之胺(成分A)或其鹽、相對於25℃之水100 g之溶解度為0.02 g以上且未達10 g之溶劑(成分B)、及水(成分D)，且上述成分A係選自碳數為6以上且26以下之一級胺、二級胺及三級胺之至少1種。 ＜2＞如＜1＞記載之網版用洗淨劑組合物，其pH值為5以上且12以下。 ＜3＞如＜1＞或＜2＞記載之網版用洗淨劑組合物，其pH值較佳為12以下，更佳為9以下，進而較佳為8以下，進而更佳為7以下。 ＜4＞如＜1＞至＜3＞中任一項記載之網版用洗淨劑組合物，其pH值較佳為4以上，更佳為4.5以上，進而較佳為5以上，進而更佳為5.5以上。 ＜5＞如＜1＞至＜4＞中任一項記載之網版用洗淨劑組合物，其中成分A之相對於25℃之水100 g之溶解度未達10 g，較佳為8 g以下，更佳為5 g以下，進而較佳為2 g以下，進而更佳為1 g以下，進而更佳為0.5 g以下，進而更佳為0.2 g以下，進而更佳為0.1 g以下。 ＜6＞如＜1＞至＜5＞中任一項記載之網版用洗淨劑組合物，其中成分A之相對於25℃之水100 g之溶解度較佳為0.0001 g以上，更佳為0.001 g以上，進而較佳為0.01 g以上。 ＜7＞如＜1＞至＜6＞中任一項記載之網版用洗淨劑組合物，其中成分A之碳數為6以上，較佳為7以上，更佳為8以上。 ＜8＞如＜1＞至＜7＞中任一項記載之網版用洗淨劑組合物，其中成分A之碳數為26以下，較佳為18以下，更佳為12以下，進而較佳為10以下。 ＜9＞如＜1＞至＜8＞中任一項記載之網版用洗淨劑組合物，其中成分A係選自下述式(I)所表示之化合物之至少1種。 [化2]
Figure 02_image003
上述式(I)中，R1 表示選自碳數5以上且18以下之直鏈或支鏈烷基、及碳數5以上且18以下之直鏈或支鏈烯基之至少1種，R2 及R3 相同或不同，表示選自碳數1以上且5以下之直鏈或支鏈烷基及氫原子之至少1種，且R1 、R2 及R3 之合計碳數為6以上且26以下。 ＜10＞如＜9＞記載之網版用洗淨劑組合物，其中成分A之鹽係選自上述式(I)所表示之化合物之至少1種化合物與選自如下化合物及甲酸之至少1種化合物的鹽，上述化合物具有1～3個選自羧基、磺酸基、硫酸基及磷酸基之至少1種基，且碳數為2以上且12以下。 ＜11＞如＜1＞至＜10＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分A之含量較佳為0.001質量%以上，更佳為0.01質量%以上，進而較佳為0.02質量%以上。 ＜12＞如＜1＞至＜11＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分A之含量較佳為2.0質量%以下，更佳為1.0質量%以下，進而較佳為0.7質量%以下，進而更佳為0.2質量%以下，進而更佳為0.15質量%以下，進而更佳為0.1質量%以下。 ＜13＞如＜1＞至＜12＞中任一項記載之網版用洗淨劑組合物，其中成分B之相對於25℃之水之溶解度為0.02 g以上，較佳為0.05 g以上，更佳為0.1 g以上，進而較佳為0.2 g以上。 ＜14＞如＜1＞至＜13＞中任一項記載之網版用洗淨劑組合物，其中成分B之相對於25℃之水之溶解度未達10 g，較佳為5 g以下，更佳為3g以下，進而較佳為2 g以下。 ＜15＞如＜1＞至＜14＞中任一項記載之網版用洗淨劑組合物，其中成分B係選自下述式(II)所表示之化合物之至少1種化合物。 R4 O-(EO)m (PO)n -H (II) 此處，式(II)中，R4 表示碳數3以上且12以下之烴基，EO表示環氧乙烷基，m為EO之加成莫耳數且為0以上且5以下之數，PO表示環氧丙烷基，n為PO之加成莫耳數且為0以上且2以下之數，m＋n≧1，EO與PO之加成形態可為嵌段亦可為無規，且EO與PO之加成順序不受限定。 ＜16＞如＜15＞記載之網版用洗淨劑組合物，其中式(II)中之R4 為碳數3以上且12以下之烴基，較佳為碳數6以上且10以下之烴基，更佳為碳數6以上且8以下之烴基。 ＜17＞如＜1＞至＜16＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分B之含量較佳為0.1質量%以上，更佳為0.5質量%以上，進而較佳為1質量%以上，進而更佳為2質量%以上。 ＜18＞如＜1＞至＜17＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分B之含量較佳為20質量%以下，更佳為15質量%以下，進而較佳為12質量%以下，進而更佳為10質量%以下。 ＜19＞如＜1＞至＜18＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物中成分A之含量相對於成分B之含量的比A/B較佳為0.001以上，更佳為0.002以上，進而較佳為0.003以上。 ＜20＞如＜1＞至＜19＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物中成分A之含量相對於成分B之含量的比A/B較佳為0.1以下，更佳為0.09以下，進而較佳為0.08以下。 ＜21＞如＜1＞至＜20＞中任一項記載之網版用洗淨劑組合物，其進而調配有選自如下化合物及甲酸之至少1種酸(成分C)，上述化合物具有1～3個選自羧基、磺酸基、硫酸基及磷酸基之至少1種基，且碳數為2以上且12以下。 ＜22＞如＜21＞記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分C之含量(或調配量)較佳為0.001質量%以上，更佳為0.005質量%以上，進而較佳為0.01質量%以上。 ＜23＞如＜21＞或＜22＞記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分C之含量(或調配量)較佳為2.0質量%以下，更佳為1.0質量%以下，進而較佳為0.7質量%以下，進而更佳為0.2質量%以下，進而更佳為0.15質量%以下，進而更佳為0.1質量%以下。 ＜24＞如＜21＞至＜23＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物中成分A之含量相對於成分C之含量(或調配量)的比A/C較佳為0.1以上，更佳為0.2以上，進而較佳為0.4以上。 ＜25＞如＜21＞至＜24＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物中成分A之含量相對於成分C之含量(或調配量)的比A/C較佳為10以下，更佳為7以下，進而較佳為5以下。 ＜26＞如＜1＞至＜25＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分D之含量較佳為70質量%以上，更佳為80質量%以上，進而較佳為85質量%以上。 ＜27＞如＜1＞至＜26＞中任一項記載之網版用洗淨劑組合物，其中洗淨劑組合物於洗淨時之成分D之含量較佳為99質量%以下，更佳為97質量%以下，進而較佳為95質量%以下。 ＜28＞一種網版之洗淨方法，其包含使用如＜1＞至＜27＞中任一項記載之洗淨劑組合物洗淨被洗淨物之步驟，且上述被洗淨物為網版印刷後之網版。 ＜29＞如＜28＞記載之網版之洗淨方法，其包含不沖洗上述洗淨後之網版而進行乾燥之步驟。 ＜30＞一種套組，其係用於製造如＜1＞至＜27＞中任一項記載之洗淨劑組合物者，且其於不使成分A、成分B及成分D中之至少1種成分與其他成分混合之狀態下保管。 ＜31＞一種如＜1＞至＜27＞中任一項記載之洗淨劑組合物之用途，其用於洗淨網版印刷後之網版。 ＜32＞一種如＜1＞至＜27＞中任一項記載之洗淨劑組合物之用途，其用於將助焊劑及焊料膏之至少一者自網版去除。 實施例 以下，藉由實施例對本發明具體地進行說明，但本發明不受該等實施例任何限定。 1.洗淨劑組合物之製備(實施例1～26及比較例1～4) 以成為下述表1中記載之組成及含量(質量%、有效成分)之方式調配各成分，獲得實施例1～26及比較例1～4之洗淨劑組合物。pH值係25℃下洗淨劑組合物之pH值，係使用pH值計(東亞電波工業股份有限公司，HM-30G)測定將電極浸漬於洗淨劑組合物中經過40分鐘後之數值。 作為洗淨劑組合物之成分，使用下述者。 ＜成分A：胺＞ ·正己胺(和光純藥工業股份有限公司製造) ·正辛胺(東京化成工業股份有限公司製造) ·正十二烷基胺(東京化成工業股份有限公司製造，十二烷基胺(Dodecylamine)) ·正硬脂胺(東京化成工業股份有限公司製造，硬脂胺(Stearylamine)) ·N-甲基己基胺(和光純藥工業股份有限公司製造) ·N,N-二甲基己基胺(和光純藥工業股份有限公司製造) ＜非成分A：胺＞ ·正丁胺(和光純藥工業股份有限公司製造) ·聚氧乙烯(2莫耳)月桂胺(青木油脂工業股份有限公司製造，BLAUNON L-202) ＜成分B：溶劑(二醇醚)＞ ·乙二醇單2-乙基己基醚[日本乳化劑股份有限公司製造，乙二醇2-乙基己基醚(EHG，2-Ethyl Hexyl Glycol)] ·二乙二醇單己醚[日本乳化劑股份有限公司製造，二乙二醇己醚(HeDG，Hexyl Diglycol)] ·苯氧基丙醇(丙二醇單苯醚)[日本乳化劑股份有限公司製造，丙二醇苯醚(PhFG，Phenyl Propylene Glycol)] ·乙二醇單己醚[日本乳化劑股份有限公司製造，乙二醇己醚(HeG，Hexyl Glycol)] ·二乙二醇單2-乙基己基醚[日本乳化劑股份有限公司製造，二乙二醇2-乙基己基醚(EHDG，2-Ethyl Hexyl Diglycol)] ·二丙二醇單丙醚[日本乳化劑股份有限公司製造，二丙二醇丙醚(PFDG，Propyl Propylene Diglycol)] ＜非成分B：溶劑＞ ·二乙二醇單丁醚[日本乳化劑股份有限公司製造，二乙二醇丁醚(BDG，Butyl Diglycol)] ＜成分C：酸＞ ·乙酸(關東化學股份有限公司製造，鹿一級) ·對甲苯磺酸(和光純藥工業股份有限公司製造，對甲苯磺酸一水合物) ·1-羥基亞乙基-1,1-二膦酸(Italmatch Chemicals公司製造，Dequest 2010，60%水溶液) ·甲酸(朝日化學工業所股份有限公司製造，甲酸88%) ·2-乙基己酸(和光純藥工業股份有限公司製造) ·檸檬酸[和光純藥工業股份有限公司製造，檸檬酸(酐)] ＜成分D：水＞ ·由Organo股份有限公司製造之純水裝置G-10DSTSET製造之1 μS/cm以下之純水 ＜其他＞ ·氫氧化鉀(關東化學股份有限公司製造，鹿特級，固形物成分48質量%) [胺及溶劑相對於水之溶解度] 於1 L玻璃燒杯中添加水500 g，一面使用轉子(氟樹脂(PTFE(Polytetrafluoroethylene，聚四氟乙烯))，f 8 mm×50 mm)以轉數100 rpm進行攪拌，一面利用25℃之恆溫槽進行保溫。添加各種胺或溶劑0.1 g，利用目視確認均勻透明之狀態。每次追加添加0.1 g各種胺或溶劑直至變得不均勻透明，測定於水中之溶解度。 此處，於即便添加50 g胺或溶劑亦均勻透明之情形時，在該時間點結束測定，判斷為相對於25℃之水100 g之溶解度為10 g以上。於添加0.1 g胺或溶劑時便不均勻透明之情形時，判斷為相對於25℃之水100 g之溶解度未達0.02 g。 2.洗淨劑組合物之評價 使用所製備之實施例1～26及比較例1～4之洗淨劑組合物進行下述評價。 [穩定性] 於100 mL玻璃燒杯中製備各洗淨劑組合物100 g，於溫度25℃下使用轉子(氟樹脂(PTFE)，f 8 mm×25 mm)以轉數100 rpm進行攪拌，對攪拌過程中之液體之狀態進行目視觀察，利用下述評價基準評價穩定性。將其結果示於表1。於未確認到相分離之情形時，可評價為穩定性優異。 ＜評價基準＞ A：無相分離 B：相分離 [洗淨性試驗方法] 於不鏽鋼製金屬網(斜紋荷蘭編織(twill dutch weave)，500目)塗佈助焊劑(MB-T100，千住金屬工業股份有限公司製造)，用助焊劑填滿不鏽鋼製金屬網之開口部，利用刮刀去除多餘之助焊劑後於室溫下放置24小時，切斷為20 mm×20 mm而製作評價用試樣。使用該試樣，按以下之順序對洗淨劑組合物之洗淨性進行評價。 於100 mL玻璃燒杯中添加各洗淨劑組合物50 g，並保溫於25℃水浴中。繼而，用鑷子保持試樣，將其浸漬於洗淨劑組合物中，照射超音波(104 kHz，50 W)15分鐘。洗淨後，不沖洗試樣而利用60℃之熱風乾燥15分鐘。 [洗淨性之評價方法] 使用光學顯微鏡：數位顯微鏡VHX-2000(KEYENCE股份有限公司製造)，目視確認於乾燥後試樣之金屬網開口部有無助焊劑殘渣，並根據下述計算式算出殘留助焊劑殘渣之開口部之殘渣率，對洗淨性進行評價。將結果示於表1。值越小，可評價洗淨性越優異。 殘渣率(%)＝有殘渣之開口部數÷全部之開口部數×100 [脫液性評價] 將鎳板(50 mm×25 mm×0.5 mm，太佑機材股份有限公司製造)作為試樣，使其垂直(將50 mm設為高度方向)立起，將洗淨劑組合物0.04 mL滴至垂直面上端，測量流至下端之到達時間，對脫液性進行評價。將結果示於表1。值越小，可評價脫液性越優異，乾燥越快。 [抑泡性] 將各洗淨劑組合物50 g添加於110 mL之螺旋口瓶，並保溫於25℃，上下振盪30次後靜置10秒，然後測量泡高度，從而對抑泡性進行評價。將結果示於表1。值越小，可評價起泡之抑制效果越高。 [表1]
Figure 106125434-A0304-0001
 如上述表1所示，含有特定之胺(成分A)、特定之溶劑(成分B)及水(成分D)之實施例1～26之洗淨劑組合物與比較例1～4之洗淨劑組合物相比，洗淨性及脫液性優異。 [產業上之可利用性] 本發明之洗淨劑組合物作為網版印刷後之網版用洗淨劑組合物有用，可縮短洗淨及乾燥所耗費之時間，效率良好地獲得潔淨度較高之網版，進而可提高高品質之印刷基板或陶瓷基板等電子零件之生產效率。The present invention is based on the following knowledge and insights: by containing in the detergent composition used for cleaning the screen plate, the solubility of 100 g of water at 25°C is less than 10 g and the carbon number is one to three from 6 to 26. A grade amine (component A) and a solvent (component B) with a solubility of 0.02 g or more and less than 10 g with respect to 100 g of water at 25°C (component B) can improve the detergency and quicken the deliquability. That is, in one aspect, the present invention relates to a detergent composition for a screen (hereinafter also referred to as "the detergent composition of the present invention"), which contains a solubility of 100 g of water at 25°C. Up to 10 g of amine (component A) or its salt, a solvent (component B) with a solubility of 0.02 g or more and less than 10 g with respect to 100 g of water at 25°C, and water, and the above component A is selected from carbon The number is at least one of a primary amine, a secondary amine, and a tertiary amine from 6 to 26. According to the present invention, it is possible to provide a cleaning composition for a screen plate having excellent cleaning properties and deliquoring properties. In addition, by using the detergent composition of the present invention, the time taken for the cleaning and drying of the screen can be shortened, and a screen with excellent cleanliness can be obtained efficiently, and further, high-quality printed substrates or ceramics can be improved The production efficiency of electronic components such as substrates. Although the detailed mechanism of the effect of the detergent composition of the present invention is not clear, it is estimated as follows. If the detergent composition of the present invention is used to clean the screen after screen printing, the amine of component A in the detergent composition has a low solubility in water and has low hydrophilicity, that is, hydrophobicity, so It is adsorbed on the surface of the screen and makes the surface of the screen hydrophobic. In addition, when the component A is hydrophobized on the screen surface, it will adsorb or permeate into the oily components such as flux, so that the fluidity of the oily component will be improved, and it will repel the surface charge of the screen. It is thought that by acting on the surface of the screen and the oily components such as flux as described above, the oily components can be peeled (removed) from the screen, thereby preventing the removed oily components from adhering to the screen again. Furthermore, it is considered that when the detergent composition is used for washing, the oily components can be easily removed from the screen with the aid of the physical force generated by spray or ultrasonic waves. It is presumed that since the oily components can be removed from the screen plate and re-adhesion can be prevented as described above, and the aggregation of the oily components can be suppressed, the detergency is improved. In addition, it is estimated that the surface of the screen is hydrophobized and/or the surface tension of the detergent composition is large, so that the liquid removal property becomes faster. In addition, it is estimated that the solvent of component B in the detergent composition has a certain degree of solubility in water, so it is compatible with component A, so that component A can be uniformly stabilized in water and is easily adsorbed or adsorbed to oily components such as flux. It penetrates, so the detergency is improved. It is further speculated that when component A forms a salt with an acid, especially when an acid (component C) is further formulated in the detergent composition of the present invention to make the amine of component A and the acid of component C form a salt, due to The detergent composition contains salts of amines and acids, and the permeability to oily components such as flux is improved, and the above effects can be exhibited in a shorter time. However, the present invention may be interpreted without being limited to this mechanism. [Component A: Amine] The detergent composition of the present invention contains an amine (component A) or a salt thereof whose solubility is less than 10 g with respect to 100 g of water at 25°C. In the present invention, Component A can be used singly or as a mixture of two or more. The solubility of component A with respect to 100 g of water at 25°C is less than 10 g. From the viewpoint of detergency and deliquability, it is preferably 8 g or less, more preferably 5 g or less, and even more preferably 2 g or less, more preferably 1 g or less, still more preferably 0.5 g or less, still more preferably 0.2 g or less, still more preferably 0.1 g or less, and from the same viewpoint, preferably 0.0001 g or more , More preferably 0.001 g or more, and still more preferably 0.01 g or more. From the viewpoint of detergency and deliquoring properties, the amine of component A is at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines having 6 or more carbon atoms and 26 or less. The carbon number of component A is 6 or more, preferably 7 or more, more preferably 8 or more from the viewpoint of detergency and deliquability, and from the same viewpoint, it is 26 or less, preferably 18 or less, more preferably 12 or less, and still more preferably 10 or less. When the component A is in the form of a salt, there are no particular limitations on the counter ion used to form the salt. For example, the acid of the component C can be mentioned. As component A, it is preferable that it is at least 1 sort(s) chosen from the compound represented by Formula (I) from a viewpoint of washing property and liquid removal property. [化1]
Figure 02_image001
In formula (I), R 1 represents at least one selected from linear or branched alkyl groups having 5 or more carbon atoms and 18 or less, and linear or branched alkenyl groups having 5 or more carbon atoms and 18 or less, R 2 And R 3 are the same or different, and represent at least one selected from linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms, and the total carbon number of R 1 , R 2 and R 3 is 6 or more And below 26. In the formula (I), the carbon number of R 1 is 5 or more, preferably 6 or more, more preferably 7 or more from the viewpoints of detergency and deliquability, and prevents foaming (hereinafter also referred to as From the viewpoint of "foam suppression"), it is 18 or less, preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. In formula (I), from the viewpoints of detergency and drainability, R 2 and R 3 are each independently at least 1 selected from linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms. One is preferably at least one selected from a linear alkyl group having 1 or 2 carbon atoms and a hydrogen atom, more preferably a methyl group or a hydrogen atom, and still more preferably a hydrogen atom. In formula (I), the total carbon number of R 1 , R 2, and R 3 is 6 or more, preferably 7 or more, and more preferably 8 or more from the viewpoint of detergency and deliquability, and From the viewpoint of foam suppression, it is 26 or less, preferably 18 or less, more preferably 12 or less, and still more preferably 10 or less. As a salt of component A, the salt of at least one compound selected from the compound represented by the said formula (I) and an acid from a viewpoint of cleaning property and liquid removal property can be mentioned. The acid is not particularly limited as long as it forms a water-soluble salt with Component A. For example, the following Component C acid can be mentioned. The content of Component A in the detergent composition of the present invention during washing is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more, and from the viewpoints of detergency, deliquability, and foam suppression, it is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.7% by mass or less, and further It is more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, and still more preferably 0.1% by mass or less. When component A is a combination of two or more amines, the content of component A refers to the total content. In the present invention, "the content of each component of the detergent composition during washing" in one or more embodiments refers to the content of each component of the detergent composition used in the washing step. [Component B: Solvent] The detergent composition of the present invention contains a solvent (component B) having a solubility of 0.02 g or more and less than 10 g with respect to 100 g of water at 25°C. In the present invention, Component B can be used singly or in combination of two or more. The solubility of component B with respect to water at 25°C is 0.02 g or more, preferably 0.05 g or more, more preferably 0.1 g or more, and still more preferably 0.2 g or more from the viewpoint of detergency and deliquability. In addition, from the same viewpoint, it is less than 10 g, preferably 5 g or less, more preferably 3 g or less, and still more preferably 2 g or less. As component B, from the viewpoints of detergency and deliquoring properties, solvents other than component A having solubility within the above range can be cited, for example, solvents selected from glycol ether based solvents having solubility within the above range can be cited And at least one of alcohol solvents. As said glycol ether solvent, it is preferable that it is at least 1 sort(s) chosen from the compound represented by following formula (II) from a viewpoint of cleaning property and liquid removal property. R 4 O-(EO) m (PO) n -H (II) In the above formula (II), R 4 represents a hydrocarbon group with a carbon number of 3 or more and 12 or less, EO represents an ethylene oxide group, and m is an addition of EO It is the number of moles and is a number from 0 to 5, PO represents a propylene oxide group, n is the number of added moles of PO and is a number from 0 to 2, m+n≧1, the addition of EO and PO The morphology can be block or random, and the order of addition of EO and PO is not limited. In the formula (II), from the viewpoint of improving the detergency and deliquability, R 4 is a hydrocarbon group having a carbon number of 3 or more and 12 or less, preferably a hydrocarbon group having a carbon number of 6 or more and 10 or less, more preferably a carbon group A hydrocarbon group having a number of 6 or more and 8 or less. In the formula (II), (EO) m (PO) n may be composed of an ethylene oxide group alone, or may be composed of an ethylene oxide group and a propylene oxide group. When (EO) m (PO) n is composed of ethylene oxide group and propylene oxide group, the arrangement of EO and PO may be random or block. When the arrangement of EO and PO is a block, as long as the number of blocks of EO and the number of blocks of PO are within the above range, each of them may be one or more. When the number of blocks containing EO is two or more, the number of repetitions of EO in each block may be the same or different. Specific examples of component B include, for example, selected from the group consisting of ethylene glycol mono-2-ethylhexyl ether (solubility: 0.20 g), diethylene glycol mono-2-ethylhexyl ether (solubility: 0.20 g), and ethylene glycol mono-2-ethylhexyl ether (solubility: 0.20 g) Alcohol monohexyl ether (solubility: 1.00 g), diethylene glycol monohexyl ether (solubility: 1.40 g), propylene glycol monophenyl ether (phenoxypropanol, solubility: 0.20 g), dipropylene glycol monopropyl ether (solubility: 5.60 g), propylene glycol monobutyl ether (solubility: 6.60 g) one or a combination of two or more. From the viewpoint of improving the deliquability, it is preferably selected from ethylene glycol mono-2-ethylhexyl ether (solubility: 0.20 g), ethylene glycol monohexyl ether (solubility: 1.00 g), diethylene glycol mono One or a combination of two or more of hexyl ether (solubility: 1.40 g) and propylene glycol monophenyl ether (solubility: 0.20 g), more preferably selected from ethylene glycol mono-2-ethylhexyl ether (solubility: 0.20 g) , Diethylene glycol monohexyl ether (solubility: 1.40 g) and propylene glycol monophenyl ether (solubility: 0.20 g) one or a combination of two or more, more preferably ethylene glycol mono-2-ethylhexyl ether ( Solubility: 0.20 g) and diethylene glycol monohexyl ether (solubility: 1.40 g), and more preferably ethylene glycol mono-2-ethylhexyl ether (solubility: 0.20 g). The solubility in parentheses indicates the solubility relative to 100 g of water at 25°C. The content of component B in the detergent composition of the present invention during washing is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more, more preferably 2% by mass or more, and from the same viewpoint, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and still more Preferably, it is 10% by mass or less. When component B is a combination of two or more solvents, the content of component B refers to the total content. The ratio A/B of the content of the component A to the content of the component B in the detergent composition of the present invention is preferably 0.001 or more, more preferably 0.002 or more, and further It is preferably 0.003 or more, and from the same viewpoint, it is preferably 0.1 or less, more preferably 0.09 or less, and still more preferably 0.08 or less. [Component C: Acid] The detergent composition of the present invention may further contain an acid (component C). In addition, the detergent composition of the present invention may be further formulated with an acid (component C). In the present invention, Component C can be used singly or as a mixture of two or more kinds. Component C is preferably an acid that forms a salt with Component A from the viewpoint of cleansing properties and deliquoring properties, and more preferably one or more acids selected from the following compounds and formic acid. The above-mentioned compounds have 1 to 3 at least one group selected from a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group, and the carbon number is 2 or more and 12 or less. Specific examples of component C include, for example, selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, capric acid, lauric acid, Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, ethanol Acid, lactic acid, hydroxymalonic acid, hydroxybutyric acid, glyceric acid, malic acid, tartaric acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, lauryl sulfate, 2-amino group Ethylphosphonic acid, 1-hydroxyethylene-1,1-diphosphonic acid, amino tris (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid) and diethylene triamine penta (Methylene phosphonic acid) is more preferably selected from formic acid, acetic acid, caprylic acid, 2-ethylhexanoic acid, lactic acid, One or a combination of two or more of citric acid, p-toluenesulfonic acid and 1-hydroxyethylene-1,1-diphosphonic acid, and more preferably selected from formic acid, acetic acid, 2-ethylhexanoic acid, lemon One or a combination of two or more of acid, p-toluenesulfonic acid and 1-hydroxyethylene-1,1-diphosphonic acid, and more preferably selected from formic acid, acetic acid, p-toluenesulfonic acid and 1-hydroxyethylene One or a combination of two or more of ethyl-1,1-diphosphonic acid, more preferably any one of acetic acid and p-toluenesulfonic acid, and still more preferably acetic acid. In the detergent composition of the present invention, the content (or blending amount) of component C during washing is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, from the viewpoints of detergency and deliquability , More preferably 0.01% by mass or more, and from the viewpoints of low cleansing properties, deliquability, and suppression of foaming, it is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and further It is preferably 0.7% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, and still more preferably 0.1% by mass or less. When the component C is a combination of two or more acids, the content (or blended amount) of the component C refers to the total content (or total blended amount) of them. The ratio A/C of the content of component A to the content (or blending amount) of component C in the detergent composition of the present invention is preferably 0.1 or more, more preferably It is 0.2 or more, more preferably 0.4 or more, and from the same viewpoint, it is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less. [Component D: Water] The detergent composition of the present invention contains water (component D). As the water of component D, ion exchange water, RO (Reverse Osmosis, reverse osmosis) water, distilled water, pure water, and ultrapure water can be used. The content of water may be appropriately set according to the usage state of the detergent composition of the present invention. From the viewpoint of detergency, the content of component D of the detergent composition of the present invention during washing is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more And, from the same viewpoint, it is preferably 99% by mass or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less. [Optional component] The detergent composition of the present invention may contain optional components in addition to the above-mentioned components A to D, within a range that does not impair the effects of the present invention. Examples of optional components include: selected from nonionic surfactants; compounds having chelating power such as amino carboxylates such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, etc. ; Preservatives; Rust inhibitors; Bactericides; Antibacterial agents; Antifoaming agents such as polysiloxane; Antioxidants; Coconut fatty acid methyl ester, benzyl acetate and other esters; Hydrocarbon solvents; One or two types of alcohols, etc. A combination of the above. From the viewpoint that the content of the optional components of the detergent composition of the present invention during washing does not hinder the effect of the present invention, it is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more, and 1.5% by mass or less, more preferably 0% by mass or more and 1.3% by mass or less, and still more preferably 0% by mass or more and 1.0% by mass or less. When the detergent composition of the present invention contains two or more optional components, the content of the optional components refers to their total content. [The pH value of the detergent composition] The pH value of the detergent composition of the present invention during washing is preferably 12 or less, more preferably 9 or less from the viewpoint of detergency and deliquability. It is more preferably 8 or less, and still more preferably 7 or less, and from the viewpoints of cleaning properties, deliquoring properties, and prevention of corrosion of cleaning equipment, it is preferably 4 or more, more preferably 4.5 or more, and still more Preferably it is 5 or more, More preferably, it is 5.5 or more. In the present invention, the "pH during washing" refers to the pH when the detergent composition is used at 25°C (after dilution), which can be measured with a pH meter. Specifically, it can be measured by the method described in the examples. For the pH adjustment of the detergent composition of the present invention, for example, inorganic acids such as nitric acid and sulfuric acid; organic acids such as hydroxycarboxylic acids, polycarboxylic acids, amino polycarboxylic acids, and amino acids; and metal salts thereof or the like can be used. Alkaline substances such as ammonium salt, ammonia, sodium hydroxide, potassium hydroxide, amine, etc. are carried out. [Manufacturing method of detergent composition] The detergent composition of the present invention can be manufactured by blending the above-mentioned component A, component B, and component D, and optionally component C and optional components by a known method. For example, the detergent composition of the present invention can be prepared by blending at least the above-mentioned component A, component B, and component D. Therefore, in one aspect, the present invention relates to a method for manufacturing a detergent composition, which includes at least the step of blending the above-mentioned component A, component B, and component D. In the present invention, the so-called "preparation" includes mixing component A, component B, component D, and optionally component C and optional components at the same time or in any order. In the manufacturing method of the detergent composition of the present invention, the blending amount of each component can be set to be the same as the content of each component of the detergent composition of the present invention described above. From the viewpoint of storage and transportation, the detergent composition of the present invention can also be prepared as a concentrate obtained by reducing the amount of water in component D. From the viewpoint of storage and transportation, the concentrate of the detergent composition is preferably made into a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably made with a dilution ratio of 200 times or less The concentrate. The concentrate of the detergent composition can be diluted with water during use so that the content of each component becomes the above-mentioned content (that is, the content during cleaning). Furthermore, the concentrate of a detergent composition can also be used by adding each component separately at the time of use. In the present invention, the "when in use" or "when washing" of the concentrate of the detergent composition refers to the state in which the concentrate of the detergent composition is diluted. [Substance to be cleaned] In one or more embodiments, the detergent composition of the present invention can be used to clean the screen after screen printing, and clean the adhered flux, solder paste, silver paste, and copper paste. And other conductive paste and other screens. Examples of the screen plate include metal masks, resin masks, electroforming masks, emulsion masks, and the like. Therefore, in one aspect, the present invention relates to the use of the detergent composition of the present invention for cleaning the screen after screen printing. Furthermore, in another aspect, the present invention relates to a use of the detergent composition of the present invention for removing at least one of flux and solder paste from the screen. [Washing method] In one aspect, the present invention relates to a method for washing a screen plate (hereinafter also referred to as "the washing method of the present invention"), which includes washing the quilt using the detergent composition of the present invention The step of washing things (hereinafter also referred to as "washing step"). When the detergent composition of the present invention is a concentrate, the cleaning method of the present invention may further include a step of diluting the concentrate of the detergent composition. As the object to be cleaned, the above-mentioned object to be cleaned may be mentioned. In one or more embodiments, the above-mentioned washing step may include contacting the detergent composition of the present invention with the object to be washed. As a method of washing an object to be cleaned using the detergent composition of the present invention, for example, a method of immersing the object to be cleaned in a washing tank and bringing the detergent composition into contact with the object to be cleaned, The method of bringing the detergent composition into contact with the object to be cleaned in the bath of the ultrasonic cleaning device, the method of spraying the detergent composition and contacting the object to be cleaned, etc. The cleaning method of the present invention may further include a step of drying the screen plate after cleaning without washing. Thereby, the time consumed for cleaning and drying of the screen can be shortened, a screen with excellent cleanliness can be obtained efficiently, and the productivity of electronic components such as high-quality printed circuit boards or ceramic substrates can be improved. In the cleaning method of the present invention, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present invention is in contact with the object to be cleaned in terms of easily exerting the cleaning power of the detergent composition of the present invention. As the ultrasonic irradiation conditions, for example, it can be set to 20 to 2000 kHz. [Set] In one aspect, the present invention relates to a set (hereinafter also referred to as "the set of the present invention"), which is used to manufacture the detergent composition of the present invention, and it is not used At least one of the component A, the component B, and the component D constituting the detergent composition of the present invention is stored in a state where it is mixed with other components. According to the present invention, it is possible to provide a set that can obtain a detergent composition excellent in detergency and deliquoring properties. As the set of the present invention, for example, the following set (two-component detergent composition) which does not mix a solution containing component B (first solution) and one of components A, C, and D Or, store in a state where two or more kinds of solutions (second solution) are mixed with each other, and mix them at the time of use. The above-mentioned optional components may be mixed with each of the first liquid and the second liquid as necessary. The present invention further relates to the following detergent composition, washing method, manufacturing method, and set. <1> A detergent composition for a screen plate containing an amine (component A) or its salt with a solubility of less than 10 g relative to 100 g of water at 25°C, and a solubility relative to 100 g of water at 25°C: 0.02 g or more and less than 10 g of solvent (component B) and water (component D), and the above component A is selected from at least one of the first amines, secondary amines and tertiary amines with a carbon number of 6 or more and 26 or less 1 kind. <2> The detergent composition for a screen plate as described in <1>, which has a pH of 5 or more and 12 or less. <3> The detergent composition for a screen plate as described in <1> or <2>, preferably has a pH of 12 or less, more preferably 9 or less, still more preferably 8 or less, and still more preferably 7 or less . <4> The cleaning composition for a screen plate as described in any one of <1> to <3>, preferably has a pH of 4 or more, more preferably 4.5 or more, still more preferably 5 or more, and still more Preferably, it is 5.5 or more. <5> The detergent composition for a screen plate as described in any one of <1> to <4>, wherein the solubility of component A with respect to 100 g of water at 25°C is less than 10 g, preferably 8 g Hereinafter, it is more preferably 5 g or less, still more preferably 2 g or less, still more preferably 1 g or less, still more preferably 0.5 g or less, still more preferably 0.2 g or less, and still more preferably 0.1 g or less. <6> The detergent composition for a screen plate as described in any one of <1> to <5>, wherein the solubility of component A with respect to 100 g of water at 25°C is preferably 0.0001 g or more, more preferably 0.001 g or more, more preferably 0.01 g or more. <7> The detergent composition for a screen plate as described in any one of <1> to <6>, wherein the carbon number of component A is 6 or more, preferably 7 or more, and more preferably 8 or more. <8> The detergent composition for a screen plate as described in any one of <1> to <7>, wherein the carbon number of component A is 26 or less, preferably 18 or less, more preferably 12 or less, and more Preferably, it is 10 or less. <9> The detergent composition for a screen plate as described in any one of <1> to <8>, wherein the component A is at least one selected from the compound represented by the following formula (I). [化2]
Figure 02_image003
In the above formula (I), R 1 represents at least one selected from linear or branched alkyl groups having 5 to 18 carbon atoms, and linear or branched alkenyl groups having 5 to 18 carbon atoms, R 2 and R 3 are the same or different, and represent at least one selected from linear or branched alkyl groups having 1 to 5 carbon atoms and hydrogen atoms, and the total carbon number of R 1 , R 2 and R 3 is 6 or more And below 26. <10> The detergent composition for screen printing as described in <9>, wherein the salt of component A is selected from at least one compound selected from the compound represented by the above formula (I) and at least one selected from the following compounds and formic acid A salt of a compound having 1 to 3 at least one group selected from a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group, and the carbon number is 2 or more and 12 or less. <11> The detergent composition for a screen as described in any one of <1> to <10>, wherein the content of component A in the detergent composition during washing is preferably 0.001% by mass or more, and more It is preferably 0.01% by mass or more, and more preferably 0.02% by mass or more. <12> The detergent composition for a screen as described in any one of <1> to <11>, wherein the content of component A in the detergent composition during washing is preferably 2.0% by mass or less, and more It is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, and still more preferably 0.1% by mass or less. <13> The detergent composition for a screen plate as described in any one of <1> to <12>, wherein the solubility of component B with respect to water at 25°C is 0.02 g or more, preferably 0.05 g or more, It is more preferably 0.1 g or more, and still more preferably 0.2 g or more. <14> The detergent composition for a screen plate as described in any one of <1> to <13>, wherein the solubility of component B in water at 25°C is less than 10 g, preferably 5 g or less, It is more preferably 3 g or less, and still more preferably 2 g or less. <15> The detergent composition for a screen plate as described in any one of <1> to <14>, wherein the component B is at least one compound selected from the compounds represented by the following formula (II). R 4 O-(EO) m (PO) n -H (II) Here, in formula (II), R 4 represents a hydrocarbon group with a carbon number of 3 or more and 12 or less, EO represents an ethylene oxide group, and m represents EO The number of added moles is 0 to 5, PO represents a propylene oxide group, n is the number of added moles of PO and is a number from 0 to 2, m＋n≧1, EO and PO The addition form can be block or random, and the order of addition of EO and PO is not limited. <16> The detergent composition for a screen as described in <15>, wherein R 4 in the formula (II) is a hydrocarbon group having 3 or more and 12 or less carbon atoms, preferably a hydrocarbon group having 6 or more and 10 or less carbon atoms , More preferably a hydrocarbon group having 6 or more and 8 or less carbon atoms. <17> The detergent composition for a screen as described in any one of <1> to <16>, wherein the content of component B in the detergent composition during washing is preferably 0.1% by mass or more, and more It is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more. <18> The detergent composition for a screen as described in any one of <1> to <17>, wherein the content of component B in the detergent composition during washing is preferably 20% by mass or less, and more It is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10% by mass or less. <19> The detergent composition for a screen as described in any one of <1> to <18>, wherein the ratio of the content of component A to the content of component B in the detergent composition is better than A/B It is 0.001 or more, more preferably 0.002 or more, and still more preferably 0.003 or more. <20> The detergent composition for a screen as described in any one of <1> to <19>, wherein the ratio of the content of component A to the content of component B in the detergent composition is better than A/B It is 0.1 or less, more preferably 0.09 or less, and still more preferably 0.08 or less. <21> The detergent composition for a screen plate as described in any one of <1> to <20>, which is further formulated with at least one acid (component C) selected from the following compounds and formic acid, wherein the compound has 1 ~3 at least one group selected from a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group, and the carbon number is 2 or more and 12 or less. <22> The detergent composition for a screen as described in <21>, wherein the content (or blending amount) of component C in the detergent composition during washing is preferably 0.001% by mass or more, more preferably 0.005 Mass% or more, more preferably 0.01 mass% or more. <23> The detergent composition for a screen as described in <21> or <22>, wherein the content (or blending amount) of component C of the detergent composition during washing is preferably 2.0% by mass or less, It is more preferably 1.0% by mass or less, still more preferably 0.7% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, and still more preferably 0.1% by mass or less. <24> The detergent composition for a screen as described in any one of <21> to <23>, wherein the ratio of the content of component A to the content (or blending amount) of component C in the detergent composition A/C is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.4 or more. <25> The detergent composition for a screen as described in any one of <21> to <24>, wherein the ratio of the content of component A to the content (or blending amount) of component C in the detergent composition A/C is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less. <26> The detergent composition for a screen as described in any one of <1> to <25>, wherein the content of component D in the detergent composition during washing is preferably 70% by mass or more, and more It is preferably 80% by mass or more, and more preferably 85% by mass or more. <27> The detergent composition for a screen as described in any one of <1> to <26>, wherein the content of component D in the detergent composition during washing is preferably 99% by mass or less, and more It is preferably 97% by mass or less, and more preferably 95% by mass or less. <28> A method for cleaning a screen plate, which includes the step of using the detergent composition as described in any one of <1> to <27> to clean an object to be cleaned, and the object to be cleaned is a net The screen after printing. <29> The method for cleaning the screen as described in <28>, which includes the step of drying the screen after washing without washing. <30> A kit used to manufacture the detergent composition described in any one of <1> to <27>, and which does not use at least 1 of component A, component B and component D Store the ingredients in a mixed state with other ingredients. <31> A use of the detergent composition as described in any one of <1> to <27>, which is used to clean the screen after screen printing. <32> A use of the detergent composition as described in any one of <1> to <27> to remove at least one of flux and solder paste from the screen. EXAMPLES Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited in any way by these examples. 1. Preparation of detergent composition (Examples 1 to 26 and Comparative Examples 1 to 4) The ingredients were formulated so as to become the composition and content (mass%, effective ingredient) described in Table 1 below to obtain examples Detergent compositions of 1 to 26 and Comparative Examples 1 to 4. The pH value is the pH value of the detergent composition at 25°C. The pH value is measured using a pH meter (Toa Denpa Co., Ltd., HM-30G) after immersing the electrode in the detergent composition for 40 minutes. As the components of the detergent composition, the following are used. <Component A: Amine> ·n-hexylamine (manufactured by Wako Pure Chemical Industries, Ltd.) ·n-octylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) · n-dodecylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 12 Alkylamine (Dodecylamine) ·N-stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd., Stearylamine) ·N-methylhexylamine (manufactured by Wako Pure Chemical Industries, Ltd.) ·N,N- Dimethylhexylamine (manufactured by Wako Pure Chemical Industries Co., Ltd.) <Non-Component A: Amine> ·N-butylamine (manufactured by Wako Pure Chemical Industries Co., Ltd.) ·Polyoxyethylene (2 mol) Laurylamine (Aoki Oil Manufactured by Industrial Co., Ltd., BLAUNON L-202) <Component B: Solvent (glycol ether)> · Ethylene glycol mono-2-ethylhexyl ether [manufactured by Japan Emulsifier Co., Ltd., ethylene glycol 2-ethylhexyl Ether (EHG, 2-Ethyl Hexyl Glycol)] ·Diethylene glycol monohexyl ether [manufactured by Japan Emulsifier Co., Ltd., diethylene glycol hexyl ether (HeDG, Hexyl Diglycol)] ·Phenoxypropanol (propylene glycol mono Phenyl ether) [manufactured by Japan Emulsifier Co., Ltd., propylene glycol phenyl ether (PhFG, Phenyl Propylene Glycol)] · Ethylene glycol monohexyl ether [manufactured by Japan Emulsifier Co., Ltd., glycol hexyl ether (HeG, Hexyl Glycol) ] ·Diethylene glycol mono-2-ethylhexyl ether [manufactured by Japan Emulsifier Co., Ltd., diethylene glycol 2-ethylhexyl ether (EHDG, 2-Ethyl Hexyl Diglycol)] ·Dipropylene glycol monopropyl ether [Japan Manufactured by Emulsifier Co., Ltd., Propyl Propylene Diglycol (PFDG, Propyl Propylene Diglycol)] <Non-component B: Solvent> ·Diethylene glycol monobutyl ether [manufactured by Japan Emulsifier Co., Ltd., diethylene glycol butyl ether ( BDG, Butyl Diglycol)] <Ingredient C: Acid> ·Acetic acid (manufactured by Kanto Chemical Co., Ltd., Deer 1st grade) ·p-toluenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., p-toluenesulfonic acid monohydrate) ·1 -Hydroxyethylene-1,1-diphosphonic acid (manufactured by Italmatch Chemicals, Dequest 2010, 60% aqueous solution) · formic acid (manufactured by Asahi Chemical Industry Co., Ltd., 88% formic acid) · 2-ethylhexanoic acid ( (Manufactured by Wako Pure Chemical Industries Co., Ltd.) ·Citric acid [manufactured by Wako Pure Chemical Industries Co., Ltd., citric acid (anhydride)] <Ingredient D: Water> ·Made of pure water device G-10DSTSET manufactured by Organo Co., Ltd. Pure water below 1 μS/cm <Others> · Potassium hydroxide (manufactured by Kanto Chemical Co., Ltd., deer special grade, solid content 48% by mass) [Amine and Solubility of the solvent with respect to water] Add 500 g of water to a 1 L glass beaker, and stir with a rotor (fluororesin (PTFE (Polytetrafluoroethylene, polytetrafluoroethylene), f 8 mm×50 mm) at a speed of 100 rpm) , One side uses a 25℃ constant temperature bath for heat preservation. Add 0.1 g of various amines or solvents, and visually confirm the uniform and transparent state. Add 0.1 g of various amines or solvents each time until it becomes non-uniform and transparent, and determine the solubility in water. Here, in the case where the amine or solvent is uniform and transparent even if 50 g of amine or solvent is added, the measurement is ended at this point in time, and it is judged that the solubility with respect to 100 g of water at 25° C. is 10 g or more. When adding 0.1 g of amine or solvent, it is not uniform and transparent, it is judged that the solubility with respect to 100 g of water at 25°C is less than 0.02 g. 2. Evaluation of detergent composition Using the prepared detergent compositions of Examples 1 to 26 and Comparative Examples 1 to 4, the following evaluations were performed. [Stability] Prepare 100 g of each detergent composition in a 100 mL glass beaker, stir at 100 rpm using a rotor (fluororesin (PTFE), f 8 mm×25 mm) at a temperature of 25°C. The state of the liquid during stirring was visually observed, and the stability was evaluated using the following evaluation criteria. The results are shown in Table 1. When phase separation is not confirmed, it can be evaluated as excellent in stability. <Evaluation criteria> A: No phase separation B: Phase separation [Detergency test method] Apply flux (MB-T100, Senju Metal Industry Co., Ltd.) on a stainless steel metal mesh (twill dutch weave, 500 mesh) Co., Ltd.), fill the openings of the stainless steel metal mesh with flux, remove the excess flux with a spatula, place it at room temperature for 24 hours, and cut it to 20 mm×20 mm to prepare evaluation samples. Using this sample, the detergency of the detergent composition was evaluated in the following procedures. Add 50 g of each detergent composition to a 100 mL glass beaker, and keep it in a water bath at 25°C. Then, the sample was held with tweezers, immersed in the detergent composition, and irradiated with ultrasonic waves (104 kHz, 50 W) for 15 minutes. After washing, dry the sample with hot air at 60°C for 15 minutes without washing the sample. [Method for evaluating cleanability] Using an optical microscope: digital microscope VHX-2000 (manufactured by KEYENCE Co., Ltd.), visually confirm whether there is flux residue in the metal mesh opening of the sample after drying, and calculate the residue according to the following calculation formula The residue rate of the opening of the flux residue was evaluated for the cleanability. The results are shown in Table 1. The smaller the value, the more excellent the detergency can be evaluated. Residue rate (%) = number of openings with residue ÷ total number of openings × 100 [Evaluation of deliquability] A nickel plate (50 mm×25 mm×0.5 mm, manufactured by Taiyou Machinery Co., Ltd.) was used as a sample. It was made to stand up vertically (50 mm in the height direction), and 0.04 mL of the detergent composition was dropped on the upper end of the vertical surface, and the arrival time to the lower end was measured to evaluate the drainability. The results are shown in Table 1. The smaller the value, the more excellent the deliquability and the faster the drying can be evaluated. [Foam suppression] Add 50 g of each detergent composition to a 110 mL screw-top bottle, keep it at 25°C, shake it up and down 30 times, then let it stand for 10 seconds, and then measure the foam height to determine the foam suppression performance. Evaluation. The results are shown in Table 1. The smaller the value, the higher the foaming suppression effect can be evaluated. [Table 1]
Figure 106125434-A0304-0001
 As shown in Table 1 above, the detergent composition of Examples 1 to 26 and the detergent composition of Comparative Examples 1 to 4 containing a specific amine (component A), a specific solvent (component B) and water (component D) Compared with the agent composition, it is superior in detergency and draining properties. [Industrial Applicability] The detergent composition of the present invention is useful as a detergent composition for screen printing after screen printing, can shorten the time taken for washing and drying, and efficiently obtain cleanliness. A high screen plate can improve the production efficiency of high-quality printed circuit boards or ceramic substrates and other electronic parts.

Claims (8)

一種網版用洗淨劑組合物，其含有相對於25℃之水100g之溶解度為2g以下之胺(成分A)或其鹽、相對於25℃之水100g之溶解度為0.1g以上且2g以下之溶劑(成分B)、及水，且上述成分A係選自下述式(I)所表示之化合物之至少1種；上述成分B係選自下述式(II)所表示之化合物之至少1種化合物；
Figure 106125434-A0305-02-0027-1
 上述式(I)中，R1表示選自碳數6以上且18以下之直鏈烷基，R2及R3相同或不同，表示甲基或氫原子，且R1、R2及R3之合計碳數為6以上且18以下；R4O-(EO)m(PO)nH (II)上述式(II)中，R4表示碳數3以上且12以下之烴基，EO表示環氧乙烷基，m為EO之加成莫耳數並為0以上且5以下之數，PO表示環氧丙烷基，n為PO之加成莫耳數並為0以上且2以下之數，m+n≧1，EO與PO之加成形態可為嵌段亦可為無規，且EO與PO之加成順序不受限定。 A detergent composition for a screen containing an amine (component A) or its salt having a solubility of 2g or less with respect to 100g of water at 25°C, and a solubility of 0.1g to 2g with respect to 100g of water at 25°C The solvent (component B) and water, and the above component A is selected from at least one compound represented by the following formula (I); the above component B is selected from at least one compound represented by the following formula (II) 1 compound;
Figure 106125434-A0305-02-0027-1
 In the above formula (I), R 1 represents a linear alkyl group having 6 or more and 18 or less carbon atoms, R 2 and R 3 are the same or different, and represent a methyl group or a hydrogen atom, and R 1 , R 2 and R 3 The total carbon number is 6 or more and 18 or less; R 4 O-(EO) m (PO) n H (II) In the above formula (II), R 4 represents a hydrocarbon group with a carbon number of 3 or more and 12 or less, and EO represents a ring Oxyethylene group, m is the number of added moles of EO and is a number from 0 to 5, PO represents a propylene oxide group, n is the number of added moles of PO and is a number from 0 to 2, m+n≧1, the addition form of EO and PO can be block or random, and the order of addition of EO and PO is not limited. 如請求項1之網版用洗淨劑組合物，其pH值為5以上且12以下。 For example, the detergent composition for a screen plate of claim 1 has a pH of 5 or more and 12 or less. 如請求項1之網版用洗淨劑組合物，其中成分A之鹽係選自上述式(I)所表示之化合物之至少1種化合物與選自碳數為2以上且12以下之化合物 及甲酸之至少1種化合物的鹽，上述碳數為2以上且12以下之化合物具有1~3個選自羧基、磺酸基、硫酸基及磷酸基之至少1種基。 The detergent composition for a screen plate according to claim 1, wherein the salt of component A is selected from at least one compound selected from the compound represented by the above formula (I) and a compound having a carbon number of 2 or more and 12 or less And a salt of at least one compound of formic acid, wherein the compound having a carbon number of 2 or more and 12 or less has 1 to 3 at least one group selected from the group consisting of carboxyl group, sulfonic acid group, sulfuric acid group, and phosphoric acid group. 如請求項1至3中任一項之網版用洗淨劑組合物，其進而調配有選自碳數為2以上且12以下之化合物及甲酸之至少1種酸(成分C)，上述碳數為2以上且12以下之化合物具有1~3個選自羧基、磺酸基、硫酸基及磷酸基之至少1種基。 Such as the detergent composition for a screen plate of any one of claims 1 to 3, which is further formulated with at least one acid (component C) selected from compounds having a carbon number of 2 or more and 12 or less and formic acid (component C), The compound whose number is 2 or more and 12 or less has 1 to 3 at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group. 一種網版之洗淨方法，其包含使用如請求項1至4中任一項之洗淨劑組合物洗淨被洗淨物之步驟，且上述被洗淨物為網版印刷後之網版。 A method for cleaning a screen, which includes the step of using the detergent composition as claimed in any one of claims 1 to 4 to clean the object to be cleaned, and the object to be cleaned is the screen after screen printing . 如請求項5之網版之洗淨方法，其包含不沖洗上述洗淨後之網版而進行乾燥之步驟。 For example, the cleaning method of the screen plate of claim 5, which includes the step of drying the screen plate after washing without washing. 一種如請求項1至4中任一項之洗淨劑組合物之用途，其用於洗淨網版印刷後之網版。 A use of the detergent composition according to any one of claims 1 to 4, which is used to clean the screen after screen printing. 一種如請求項1至4中任一項之洗淨劑組合物之用途，其用於將助焊劑及焊料膏之至少一者自網版去除。 A use of the detergent composition according to any one of claims 1 to 4, which is used to remove at least one of flux and solder paste from a screen.
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