WO2006090529A1 - Resin remover - Google Patents

Abstract

Disclosed is a remover for removing or cleaning a resin or resin composition from a solid surface. The remover contains 1-100 parts by mass of an epoxy compound represented by the general formula (I) below per 100 parts by mass of one or more organic solvents. (In the formula, R represents a hydrocarbon group having 1-18 carbon atoms; R1-R8 independently represent a hydrogen atom or a methyl group; p represents 0 or 1; and m and n independently represent 0, 1 or 2.)

Description

 Specification

 Resin remover

 Technical field

 [0001] The present invention relates to a remover containing a specific epoxy compound and used for removing or washing a solid surface strength resin or a resin composition.

 Background art

 [0002] In the manufacture and use of a resin or a resin composition, a cleaning agent mainly composed of an organic solvent is used to remove the resin adhering to containers, equipment, piping, products and the like. The For example, Patent Document 1 reports a cleaning agent containing γ-petit-mouth rataton, and Patent Document 2 discloses a mixture of a ketone solvent and a soot or an ester solvent and an ether solvent. A cleaning agent comprising a nitrogen-containing compound is reported in Patent Document 3.

 [0003] Negative or positive resists are used for patterns such as printed circuit boards, electronic circuit wiring such as ICs, display element color filters, and CCD color filters. Alcohol-based, ether-based, and ester-based solvents are used as organic-based removers (developers, stripping solutions) for removing the cured or uncured resist composition used in these.

 [0004] The organic solvent-based cleaning agent or removing agent has a problem in that the residual liquid is volatilized and the resin residue adheres to the solid surface. In addition, a cleaning agent or a removing agent using an alkaline compound such as a nitrogen-containing compound is a solid after the removal of the resin, because the decomposition product of the resin or the alkaline compound remains on the solid surface from which the resin has been removed. The use of the surface may have an adverse effect.

 Patent Document 1: Japanese Patent Application Laid-Open No. 8-117707

 Patent Document 2: JP-A-8-165496

 Patent Document 3: Japanese Patent Laid-Open No. 2001-518552

 Disclosure of the invention

Problems to be solved by the invention [0006] Therefore, an object of the present invention is to provide a remover for removing or washing a rosin or rosin composition from a solid surface, and after removing the rosin or rosin composition having a large removal effect. An object of the present invention is to provide a remover that does not affect the use of the body surface.

 Means for solving the problem

[0007] As a result of repeated studies, the present inventors have found that a specific epoxy compound is useful for removing a resin component.

[0008] The present invention has been made on the basis of the above findings, and is a remover for removing or washing the rosin or the rosin composition from the solid surface, and 100 parts by mass of one or more kinds of organic solvents. An epoxy compound represented by the following general formula (I) 1 to: provides a remover containing LOO parts by mass.

[0009] [Chemical 1]

(In the formula, R represents a hydrocarbon group having 1 to 18 carbon atoms, and R i ^ R ⁸ each independently represents a hydrogen atom.

 Child or methyl group, p represents 0 or 1, m and n each independently represents 0, 1 or 2;

 To express. The best mode for carrying out the invention

In the above general formula (I), the hydrocarbon group having 1 to 18 carbon atoms represented by R, when p is 0, includes a benzene ring, a cycloalkane ring, a cycloalkene ring, etc. in the chain. Alkyl group which may have a hydrocarbon ring, alkenyl which may have a hydrocarbon ring such as a benzene ring, a cycloalkane ring and a cycloalkene ring in a chain which may be linear or branched A hydrocarbon group such as a benzene ring, a cycloalkane ring, a cycloalkene ring or the like, a alkynyl group, a cycloalkyl group, and an aryl group. Among these, an alkyl group and an aryl group are preferable in that the epoxy compound is inexpensive and chemically stable.

In addition, as the hydrocarbon group having 1 to 18 carbon atoms represented by R, when p is 1, a benzene ring, a cycloalkane ring, a cycloalkene in a chain that may be linear or branched. An alkanedyl group which may have a hydrocarbon ring such as a ring, or a hydrocarbon ring such as a benzene ring, a cycloalkane ring or a cycloalkene ring in a chain which may be linear or branched Alkenes that may be Diyl group, hydrocarbon chain such as benzene ring, cycloalkane ring, cycloalkene ring, etc. in a chain which may be straight chain or branched, alkyne diyl group, cycloancandiyl group and arylene group Among these, an alkanedyl group and an arylene group are preferable in that the epoxy compound is inexpensive and chemically stable.

 [0011] R is preferred when p is 0! /, And the above alkyl group is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, Tertiary amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, iso-octyl , Tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, benzyl, phenethyl, 2-phenylpropane-2-yl, diphenylmethyl , Styryl, cinnamyl and the like.

 As in the case of the alkyl group, the aryl group, which is a preferred group for R when p is 0, includes phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-isopropyl. Phenol, 4-Isopropyl, 4-Butyl, 4-Isobutyl, 4 Tertiary, 4-Hexyl, 4-Cyclohexyl, 4-Octyl , 4- (2-ethylhexyl) phenol, 2,3 dimethylphenyl, 2,4 dimethylphenyl, 2,5 dimethylphenyl, 2,6-dimethyldimethyl, 3,4 dimethylphenol, 3,5 dimethylphenol 2,4 ditertiary butylphenyl, 2,5 ditertiarybutylphenyl, 2,6 ditertiarybutylphenyl, 2,4 ditertiarypentylphenyl, 2,5 ditertiary amylfel, cyclohexylphenyl Le, bihuel, 2, 4, 5 Trimethylphenol and the like.

[0012] The above alkanediyl group, which is a preferred group as R when p is 1, can also introduce a diol compound force. Examples of the dioly compound include ethylene glycol, 1,2 propanediol, 1,3 propanediol, 2-methyl-1,3 propanediol, 2 butyl-2-ethyl-1,3 propanediol, 1,4 butanediol, Neopentyl glycol, 3-methyl-2,4 pentanediol, 2,4 pentanediol, 1,5 pentanediol, 3-methyl-1,5 pentanediol, 2-methi Lu 2, 4-pentanediol, 2, 4-jetyl 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-otatandiol, 2 — Aliphatic diol compounds such as methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol; and cycloaliphatic diol compounds such as cyclohexanedimethanol, cyclohexanediol, and hydrogenated bisphenol A It is done. Among these, an alkanediyl group having 2 to 8 carbon atoms in which a diol compound strength is introduced is particularly preferable.

 Similarly to the alkanedyl group, the arylene group, which is a preferred group as R when p is 1, can also introduce dihydroxy aromatic compound power. Examples of the dihydroxy aromatic compound include resorcin, catechol, hydroquinone, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-tert-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 3-methyl hydroquinone, 3-ethyl hydroquinone, 3-propyl hydroquinone, 3-butyl hydroquinone, 3-tert-butyl hydroquinone, 3-phenyl hydroquinone, 3-tamyl hydroquinone, 4, 4 ' Dihydroxyaryl compounds such as dihydroxydiphenyl; bis (1, 1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. Hydroxyaryl) cycloalkanes; bis (4-hydroxyphenol) methane, 1 , 1-bis (4-hydroxyphenol) ethane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,3-bis (4-hydroxyphenol) propane, 2, 2-bis (4 —Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenol) propan, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis ( Bis (hydroxyaryl) such as 4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,4-bis (4-hydroxyphenol 2-methyl) butane Examples include alkanes.

 [0013] In the general formula (I), m and n are each independently 0, 1 or 2. Epoxy compound strength in which m and n in the general formula (I) are each independently 0 or 1. This is preferable because it is suitable for washing.

[0014] The content of the epoxy compound represented by the general formula (I) in the removing agent of the present invention is 1 to L00 parts by mass with respect to 100 parts by mass of the organic solvent. Less than 1 part by mass is sufficient The use effect cannot be obtained, and even if the amount exceeds 100 parts by mass, the use effect is not further improved. The content of the epoxy compound represented by the general formula (I) is preferably 10 to 85 parts by mass, more preferably 20 to 75 parts by mass.

[0015] Preferred and specific examples of the epoxy compound represented by the general formula (I) according to the present invention include

And Compound Nos. 1 to 45 shown below.

[Chemical Formula 2] Compound Compound Compound Compound

H 0— Cll ₂ — CI, 【CC ₁₂ H ₂ -0 ~ CH-CH-CH ₂ C _{13 r} 0— C — CH_CH ₂ C "ll, _r U— (H ₂ — CH—C 【【 ₂

 Compound Compound Compound Compound N

: ₁₅ H _3r o-cH-cH-cH ₂ c _IC [[ ₃ oc [i cif-c [i ₂ C ₅ —0— CK “(^ ((c _{1 £} ¾ _r o— CH ₂ — i CK ₂

 0 0 0 0

[0017] [Chemical 3] Compound N ′ Compound L7

C ₄ H— 0-CH— CH-0— CH— CH-CH, CgH, ~ 0 ~ CH— CH "0— CH— CH” CH ₂ C _S H ₁₇ — 0— C — CH— 0— CH ₂ — CH-CH ₂ Compound Compound Compound

C ₁₂ H ₂ — 0-CH— CH-0— CH ₂ -CH-.CH ₂ C ₁₄ H ₂₉ — 0— C? H 0— C — C [; [CH ₂ C ₁₆ H ₃₃ — 0— CH ₂ — H_0— CH ₂ — CFi_CH ₂

CH ₃ 0 CH ₃ 0 CH ₃ 0 Compound

 Compound

_{~ - 0 ~ H "C -0-} CH- CH" CH 2 Compound

H ₃ C— ( _j :--0— CH— CH-0— 'CH— ti-CH.

CH ₃

[0018] [Chemical 4]

Tomb [] Compound No. 44

— CH „— 0— CH— CH ₂ — HI 0— CH-CH— 0— C¾— CH-CH,

0 CH ₃ c¾, o '' Compound No. 45

CH-CH— CH— 0— CH— CH— CH— Ό— CH ₂ -CH— 0— CH— CH-CH ₂ 0 C¾ 'at,, ⁰ '

[0022] The organic solvent used in the removing agent of the present invention is not particularly limited, and a known general organic solvent can be used. Examples of the organic solvent include alcohol solvents, polyol solvents, ketone solvents, ester solvents, ether solvents, polyether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorine. Examples thereof include hydrocarbon solvents having a cyano group, pyrrolidone solvents, and the like, and these can be used alone or in combination of two or more. In particular, the epoxy compound represented by the general formula (I) can be stably dissolved, is inexpensive, and has a large removal effect on the resin or resin composition. It is preferable to use a ketone solvent and a Z or C 2-18 ester solvent. It is preferable to use the ketone solvent in an organic solvent at 50 to: LO 0% by mass, particularly 50 to 90% by mass. The ester solvent is preferably 10 to in an organic solvent: LOO% by mass, particularly 10 to 50%. It is preferable to use mass%.

 [0023] Preferably used as the removal agent of the present invention is a C3-C18 ketone solvent which is an organic solvent, such as acetone, ethyl methyl ketone, methyl propyl ketone, methyl isopropyl ketone, butyl methyl ketone, Isobutyl methyl ketone, sec-butyl methyl ketone, tributyl methyl ketone, jetyl ketone, 2-heptanone, 3-heptanone, dibutyl ketone, diisoptyl ketone, di-tert-butyl ketone, cyclopentanone, cyclohexanone, 4-methylhexanone and the like can be mentioned. These may be used alone or in combination of two or more.

[0024] In addition, as a preferable organic solvent used in the removing agent of the present invention having 2 to 18 carbon atoms, methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, acetic acid acetate, Butyl, isobutyl acetate, 2 butyl acetate, 3 butyl acetate, amyl acetate, isoamyl acetate, 3 amyl acetate, phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, propionate 2 butyl acid, 3 butyl propionate, amyl propionate, propion Isoamyl acid, tertiary amyl propionate, propionate phenol, methyl lactate, ethyl lactate, methyl methoxypropionate, methyl ethoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate Diethylene glycol monomethenoyl etherate acetate, ethylene glycol monoethanolate acetate, ethylene glycol monopropenoate etherate acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl etherate Teracetate, ethylene glycol mono-tert-butyl ether acetate, ethylene glycol mono-isobutyl ether acetate, ethylene glycol mono-tert-butyl ether , Propylene glycol monomethyl ether acetate, propylene glycol monoethylenoate acetate, propylene glycol monopropinoate etherate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutinoate acetate, propylene Glycolanol monobutylene etherate acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono tertiary butyl ether acetate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether acetate, butylene glycol monoethyl ether pill ether Acetate, butylene glycol monoisopropyl ether acetate, butylene Ricohone Monobutinoleate Noleacetate, Butylene Glycolone Mono Second Butyl Ether Acetate, Butylene Glycol Monoisobutyl Ether Acetate, Butylene Glycol Mono Tertiary Butyl Ether Acetate, Methyl Acetate Acetate, Ethyl Acetate Acetate, Methyl Oxobutanoate, Oxobutane Examples include oxyl, γ-latathon, and δ-latathon. These may be used alone or in combination of two or more. In addition to the epoxy compound represented by the general formula (I) and the organic solvent, various additives may be used as necessary for the removing agent of the present invention. Examples of the additive include alkaline compounds such as inorganic alkali compounds, organic amines, ammonia and quaternary ammonium salts; acidic compounds such as organic acids; viscosity modifiers; leveling agents; Agents; anti-gelling agents; dispersion stabilizers; antistatic agents; surfactants such as ionic surfactants and nonionic surfactants; water and the like. The amount of these additives to be used is appropriately selected according to the type of additive to be used, etc., but the total amount of all additives is usually 20 parts per 100 parts by mass of the organic solvent. It selects from the range used as the mass part or less.

 [0026] Applications of the remover of the present invention include cleaning of a resin composition for sealants used for ICs, printed wiring boards, etc., and a resin composition adhering to plastic processing equipment such as molds and processing machines. Cleaning of products, cleaning of mixing or manufacturing apparatus for mixing or manufacturing a resin or a resin composition, a developing solution of photoresist, a stripping solution of photoresist, cleaning of a photoresist apparatus, and the like.

 Example

 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited by the following examples.

 [Examples 1 to 8 and Comparative Example 1]

 A 30 mm × 50 mm × lmm SUS304 plate was dip coated with the black resin composition produced by the following production method to prepare a test piece. The test piece was immersed in a remover sample (see Tables 1 to 3) for 60 seconds. At this time, while the test piece was immersed, the remover sample was stirred with a magnetic stirrer. After pulling up the test piece, the surface condition was observed. Also, stick to the surface of the specimen! / Transfer the black fat composition to cellophane tape, measure the OD value of the cellophane tape before and after transfer with a Macbeth densitometer (Macbeth RD-933 type), and calculate the increase (A OD) did. The results are shown in Tables 1-3.

 [0029] (Method for producing black resin composition)

1, 1 Bis (4, 1 epoxypropyloxyphenyl) 1— (1 ”biphenyl) 1— 43 g of cyclohexylmethane, l lg acrylate, 2, 6 di tert-butyl p cresol 05 g, tetrabutylammonium acetate 0.1 l lg and propylene glycol-1 —monomethyl ether-2 acetate 23 g were charged and stirred for 16 hours at 120 ° C. Cooled to room temperature, propylene glycol-1-monomethyl ether-2 35 g of acetate and 9.4 g of biphenyltetracarboxylic dianhydride were added and stirred for 8 hours at 120 ° C. Further, tetrahydroanhydranoic anhydride 6. Calored Og at 120 ° C. for 4 hours. 3 hours at 100 ° C [¾, stirred at 80 ° C for 4 hours, 60 ° C for 6 hours, and 40 ° C for 11 hours, and then added 29 g of propylene glycol-1-monomethyl ether-2-acetate To 12g of this composition, Trimethylolpropane tri Atari rate 8 g, benzophenone 1. 8 g, carbon black (Mitsubishii匕 “MA100” manufactured by Gakusha Co., Ltd. (3.2 g) and ethyl acetate mouthsolve (75 g) were added and stirred well to obtain a black moon cake composition.

[table 1]

 * B y k—Che m i e

[0031] [Table 2]

 [0032] [Table 3]

[0033] As is apparent from Tables 1 to 3, the organic solvent contains a specific epoxy compound. When the removing agent of the present invention is used, the solid surface is uniformly washed, and there are few resin compositions remaining on the solid surface (Examples 1 to 8). On the other hand, when a remover that does not contain the specific epoxy compound according to the present invention is used, the solid surface is not evenly washed and becomes patchy, and there are many rosin compositions remaining on the solid surface (Comparative Example 1). .

Industrial applicability

 According to the present invention, it is possible to provide a remover without affecting the use of the solid surface after removing the resin or the resin composition having a large removal effect.

Claims

Claims [1] Solid surface force A removal agent for removing or washing the greaves or greaves composition, represented by the following general formula (I) in 100 parts by mass of one or more organic solvents A removal agent comprising 1 to 100 parts by mass of an epoxy compound.  [Chemical 1] (I)

(Wherein R represents a hydrocarbon group having 1 to 18 carbon atoms, R i R ⁸ each independently represents a hydrogen atom or a methyl group, p represents 0 or 1, m and n Each independently represents 0, 1 or 2.) [2] The removing agent according to claim 1, which is a group selected from hydrocarbon basic force alkanedyl group and arylene basic force having 1 to 18 carbon atoms represented by R in the general formula (I). . [3] The remover according to claim 1 or 2, wherein in the general formula (I), m and n are each independently 0 or 1. [4] The removing agent according to any one of claims 1 to 3, wherein the organic solvent contains 50% by mass or more of a ketone solvent having 3 to 18 carbon atoms. [5] The removing agent according to any one of claims 1 to 4, wherein the organic solvent contains 10% by mass or more of an ester solvent having 2 to 18 carbon atoms.