TWI384066B - Resin removal agent - Google Patents

Description

Resin remover

The present invention relates to a remover comprising a specific epoxy compound and used for removing or cleaning a resin or resin composition from a solid surface.

In the production and use of the resin or resin composition, in order to remove the resin adhering to the container, the device, the piping, the product, or the like, a cleaning agent mainly composed of an organic solvent is used. For example, Patent Document 1 discloses a cleaning agent containing γ-butyrolactone, and Patent Document 2 discloses a cleaning agent containing a mixture of a ketone solvent and/or an ester solvent and an ether solvent. Patent Document 3 discloses a cleaning agent containing a nitrogen-containing compound.

Further, a positive or negative resist is used for patterning of a printed wiring board, an electronic circuit wiring such as an IC, a color filter for a display element, and a color filter for CCD. An organic-based remover (developing liquid or peeling liquid) for removing the hardened or uncured resist composition used is an alcohol-based, ether-based or ester-based solvent.

The organic solvent-based cleaning agent or the removing agent has a problem that the residual resin is volatilized and the resin residue adheres to the solid surface. Further, when a cleaning agent or a removing agent of a basic compound such as a nitrogen-containing compound is used, a decomposition product or a basic compound of the resin remains on the surface of the solid from which the resin has been removed, and thus, when used on a solid surface after removing the resin, sometimes Can have adverse effects.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Accordingly, it is an object of the present invention to provide a remover which is used for removing or cleaning a resin or resin composition from a solid surface, which has a better removal effect and does not affect and remove the solid after the resin or resin composition. Use of the surface.

The inventors of the present invention have conducted repeated studies and found that a specific epoxy compound can be used for removing the resin component.

The present invention has been accomplished based on the above findings, and provides a remover characterized in that it is used for removing or washing a resin or resin composition from a solid surface, and is contained in 100 parts by mass or more of an organic solvent. It is composed of 1 to 100 parts by mass of an epoxy compound represented by the following formula (I).

(wherein R represents a hydrocarbon group having 1 to 18 carbon atoms, R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, p represents 0 or 1, and m and n each independently represent 0, 1 or 2.)

In the above formula (1), as for the hydrocarbon group having 1 to 18 carbon atoms represented by R, when p is 0, there may be mentioned a benzene ring, a cycloalkane ring or a cycloolefin in the chain. An alkyl group of a cyclic hydrocarbon ring; may also have a branch in a straight chain, and may have an alkenyl group of a hydrocarbon ring such as a benzene ring, a cycloalkane ring or a cycloolefin ring; and may have a branch in a straight chain, and The chain may have an alkynyl group such as a benzene ring, a cycloalkane ring or a cycloolefin ring; a cycloalkyl group and an aryl group; among these, in view of the fact that the epoxy compound is inexpensive and chemically stable, Good is alkyl or aryl.

Further, as for the hydrocarbon group having 1 to 18 carbon atoms represented by R, when p is 1, the chain may have a branch, and the chain may have a benzene ring, a cycloalkane ring or a ring. The alkyl group of the hydrocarbon ring such as an olefin ring; the chain may also have a branch, and the chain may also have an alkenylene group of a hydrocarbon ring such as a benzene ring, a cycloalkane ring or a cycloalkene ring; a chain, and the chain may have an alkynylene group such as a benzene ring, a cycloalkane ring or a cycloolefin ring, a cycloalkylene group and an exoaryl group, etc., among which the epoxy compound is considered to be inexpensive, and In terms of chemical stability, an alkyl group and an aryl group are preferred.

The above-mentioned alkyl group which is a preferred group for R when p is 0 may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group or an isobutyl group. , pentyl, isopentyl, third amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, Third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, decyl, dodecyl, tridecyl, tetradecyl, ten Pentaalkyl, hexadecyl, heptadecyl, octadecyl, benzyl, phenethyl, 2-phenylpropan-2-yl, benzhydryl, styryl, cinnamyl and the like.

Further, the same as the above-mentioned alkyl group, when p is 0, a preferred group of R, that is, the above aryl group, may be phenyl, naphthyl, 2-methylphenyl or 3-methylphenyl. 4-methylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4- Hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-Dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylbenzene , 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-pentylphenyl , cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl and the like.

In the case where p is 1, the above-mentioned alkylene group which is a preferred group of R may be introduced from the diol compound. Examples of the diol compound include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 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-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7- Heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, etc. An aliphatic diol compound; an alicyclic diol compound such as cyclohexane dimethanol, cyclohexane diol or hydrogenated bisphenol A. Among these, particularly preferred is an alkylene group introduced from a diol compound having 2 to 8 carbon atoms.

Further, in the case where p is 1, the above-mentioned exoaryl group, which is preferably the same as the above-mentioned alkylene group, can be introduced from the dihydroxy aromatic compound. Examples of the hydroxyaromatic compound include resorcinol, catechol, hydroquinone, 3-methyl resorcinol, 3-ethyl resorcinol, and 3-propyl group. Hydroquinone, 3-butyl resorcinol, 3-tert-butyl resorcinol, 3-phenyl resorcinol, 3-isopropylphenyl resorcinol, 3-methyl-p-benzene Diphenol, 3-ethylhydroquinone, 3-propyl hydroquinone, 3-butyl hydroquinone, 3-tert-butyl hydroquinone, 3-phenyl hydroquinone, a dihydroxyaryl compound such as 3-isopropylphenyl hydroquinone or 4,4'-dihydroxydiphenyl; 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-double Bis(hydroxyaryl)cycloalkanes such as (4-hydroxyphenyl)cyclohexane; bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2 - bis(4-hydroxyphenoxy)ethane, 1,3-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyl -3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)isobutane, 2,2-dual ( 4-hydroxyphenyl)butane, 2,4-bis (4- A bis(hydroxyaryl)alkane such as hydroxyphenyl 2-methyl)butane.

Further, in the above formula (I), m and n are each independently 0, 1, or 2. The epoxy compound in which m and n are each independently 0 or 1 in the above formula (I) is preferred because it has a large fluidity and is suitable for washing.

In addition, the content of the epoxy compound represented by the above formula (I) in the removing agent of the present invention is from 1 to 100 parts by mass based on 100 parts by mass of the organic solvent. If it is less than 1 part by mass, a sufficient use effect cannot be obtained, and even if it exceeds 100 parts by mass, no further improvement in the use effect is observed. The content of the epoxy compound represented by the above formula (I) is preferably from 10 to 85 parts by mass, more preferably from 20 to 75 parts by mass.

Preferred examples of the epoxy compound represented by the above formula (I) according to the present invention include the following compounds No. 1 to No. 45.

Further, the organic solvent used in the removing agent of the present invention is not particularly limited, and a well-known ordinary organic solvent can be used. Examples of the organic solvent include an alcohol solvent, a polyol solvent, a ketone solvent, an ester solvent, an ether solvent, a polyether solvent, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, and a chlorine system. The solvent, the hydrocarbon solvent having a cyano group, and the pyrrolidone solvent may be used alone or in combination of two or more. In particular, since the epoxide shown in the above formula (I) can be stably dissolved, the price is low, and the effect of removing the resin or the resin composition is large, it is preferred to use a carbon number of 3 to 18. A ketone solvent and/or an ester solvent having 2 to 18 carbon atoms. The ketone solvent is preferably 50 to 100% by mass in the organic solvent, particularly preferably 50 to 90% by mass. The ester solvent is preferably from 10 to 100% by mass, particularly preferably from 10 to 50% by mass, based on the organic solvent.

As the preferred organic solvent to be used in the remover of the present invention, that is, a ketone solvent having 3 to 18 carbon atoms, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, and butyl group are exemplified. Ketone, isobutyl methyl ketone, 2, butyl methyl ketone, 3 butyl methyl ketone, diethyl ketone, 2-heptanone, 3-heptanone, dibutyl ketone, diisobutyl ketone, dibutyl Ketone, cycloheptanone, cyclohexanone, 4-methylhexanone, and the like. These may be used singly or in combination of two or more.

Further, examples of the ester solvent having 2 to 18 carbon atoms which are preferably used in the organic solvent of the solvent of the present invention include methyl formate, ethyl formate, methyl acetate, ethyl acetate and isopropyl acetate. Ester, butyl acetate, isobutyl acetate, 2 butyl acetate, 3 butyl acetate, amyl acetate, isoamyl acetate, 3 pentyl acetate, phenyl acetate, methyl propionate, propionic acid B Ester, isopropyl propionate, butyl propionate, isobutyl propionate, 2 butyl propionate, 3 butyl propionate, amyl propionate, isoamyl propionate, 3 pentyl propionate , phenyl propionate, methyl lactate, ethyl lactate, methyl methoxypropionate, methyl ethoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol Ether acetate, diethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol isopropyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol second Butyl ether acetate, ethylene glycol isobutyl ether acetate, ethylene glycol third butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol isopropyl ether vinegar Ester, propylene glycol butyl ether acetate, propylene glycol 2 butyl ether acetate, propylene glycol isobutyl ether acetate, propylene glycol 3 butyl ether acetate, butanediol methyl ether acetate, butane diol ether acetate, butanediol C Ether acetate, butanediol isopropyl ether acetate, butanediol butyl ether acetate, butanediol second butyl ether acetate, butanediol isobutyl ether acetate, butanediol third butyl ether acetate, Ethyl acetate, ethyl acetate, methyl oxobutyrate, ethyl oxobutyrate, γ-lactone, δ-lactone, and the like. These may be used singly or in combination of two or more.

In the removal agent of the present invention, in addition to the epoxy compound described in the above formula (I) and the above organic solvent, various additives may be used as needed. Examples of the additive include basic compounds such as an inorganic base compound, an organic amine, ammonia, and a quaternary ammonium salt; an acidic compound such as an organic acid; a viscosity modifier; a homogenizing agent; an antifoaming agent; and an antigelling agent; Dispersion stabilizer; antistatic agent; surfactant such as ionic surfactant, nonionic surfactant; water, etc. The amount of the additives to be used is appropriately selected in accordance with the type of the additive to be used, and is usually selected in the range of 20 parts by mass or less based on 100 parts by mass of the total amount of the organic solvent.

For the use of the remover of the present invention, the resin composition used as a sealant in an IC or a printed wiring board is cleaned, and the resin composition is attached to a plastic processing equipment such as a metal mold or a processing machine. Cleaning, cleaning of a mixing or manufacturing apparatus for mixing or manufacturing a resin or a resin composition, development of a photoresist of a photoresist, peeling of a photoresist, cleaning of a photoresist apparatus, and the like.

[Examples]

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

[Examples 1 to 8 and Comparative Example 1]

A black resin composition produced by the following production method was immersed and coated on a SUS304 plate of 30 mm × 50 mm × 1 mm to prepare a test piece. The test piece was immersed in the remover sample (refer to Tables 1 to 3) for 60 seconds. At this time, during the impregnation of the test piece, the sample was removed by stirring with a magnetic stirrer. After taking out the test piece, observe the surface state. Further, the black resin composition attached to the surface of the test piece was transferred to a cellophane tape, and the OD value of the cellophane tape before and after the transfer was measured by a Markbes concentration meter (Model RD-933 manufactured by Markbeth) to calculate the increment. (ΔOD). The results are shown in Tables 1-3.

(Manufacturing method of black resin composition)

Add 43 g of 1,1-bis(4'-glycidoxyphenyl)-1-(1'-biphenyl)-1-cyclohexanemethane, 11 g of acrylic acid, 0.05 g of 2,6-di- Tributyl-p-cresol, 0.11 g of tetrabutylammonium acetate and 23 g of propylene glycol-1-methyl ether-2-acetate 23 g were stirred at 120 ° C for 16 hours. After cooling to room temperature, 35 g of propylene glycol-1-methyl ether-2-acetate and 9.4 g of biphenyltetracarboxylic acid dianhydride were added, and the mixture was stirred at 120 ° C for 8 hours. Further, 6.0 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C for 4 hours, at 100 ° C for 3 hours, at 80 ° C for 4 hours, at 60 ° C for 6 hours, and at 40 ° C for 11 hours, and then added. 29 g of propylene glycol-1-methyl ether-2-acetate. 8 g of trimethylolpropane triacrylate, 1.8 g of benzophenone, 3.2 g of carbon black ("MA100" manufactured by Mitsubishi Chemical Corporation) and 75 g of ethyl cellosolve were thoroughly stirred in 12 g of the composition. A black resin composition was obtained.

As shown in Tables 1 to 3, when the removing agent of the present invention containing a specific epoxy compound in an organic solution is used, the solid surface is uniformly washed, and the resin composition remaining on the solid surface is less (Example 1) ~8). On the other hand, when a remover which does not contain the specific epoxy compound of the present invention is used, the solid surface cannot be uniformly washed and formed into a patch shape, and the resin composition remaining on the solid surface is also large (Comparative Example 1).

[Industrial availability]

According to the present invention, it is possible to provide a removing agent which has a large removal effect and which does not affect the use of the solid surface after the resin or resin composition is removed.

Claims (3)

A removing agent for removing or washing a resin or a resin composition from a solid surface, the removing agent being contained in 100 parts by mass or more of the organic solvent, and containing 1 to 100 parts by mass represented by the following chemical formula (I) The epoxy compound: The removing agent according to claim 1, wherein the organic solvent contains 50% by mass or more of a ketone solvent having 3 to 18 carbon atoms. The removal agent of claim 1, wherein the organic solvent contains 10% by mass or more of an ester solvent having 2 to 18 carbon atoms.