TWI378950B - Carboxyl group-containing compounds - Google Patents

Description

1378950 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a compound containing a carboxyl group. More specifically, the present invention relates to a carboxyl group-containing compound which is used in a photosensitive resin composition for use in, for example, a coating material, an ink, an adhesive, an insulating material, and the like, and a photosensitive resin composition using the same. [Prior Art] Generally, in the photosensitive resin composition, a polyfunctional acrylic monomer and an oligomer are used in order to control the curability thereof (for example, refer to Patent Document 1). However, in the case of using a polyfunctional acrylic monomer or the like, the curing property of the photosensitive resin composition is improved, but the viscosity generated on the formed film is liable to remain. Since the solubility of the alkaline developing solution used in the subsequent step is inferior, the amount of development residual and the use of the developing liquid is increased, so that there is a disadvantage that complicated waste water treatment is required. SUMMARY OF THE INVENTION The present invention has been made in view of the above-described prior art, and an object thereof is to provide a carboxyl group-containing compound which has excellent photocurability, is difficult to remain on a formed film, and has excellent alkali solubility, and is used. A photosensitive resin composition thereof. Means for Solving the Problems The present invention relates to: Π]-a compound containing a carboxyl group, which is represented by the formula (:): 113376.doc (H2C=C(R1)COO)mX-(OCOCH(R,)CH2S( R2)COOH)n (I) (wherein R1 represents a hydrogen atom or a fluorenyl group, and R2 represents a radical having a carbon number of 丨~12] X represents an organic group having an m+n valence of 3 to 60 carbon atoms, m +n represents the valence of X, m represents an integer of 2 to 18, and n represents an integer of 1 to 3; and [2] is a photosensitive resin composition containing the above-mentioned compound having a carboxyl group. EFFECTS OF THE INVENTION The carboxyl group-containing compound of the present invention and the photosensitive resin composition using the same exhibit excellent photocurability and are excellent in alkali solubility in the formed film. [Embodiment] The compound containing a carboxyl group of the present invention is a compound represented by the formula (1) as described above: (H2C-C(R,)COO)mX-(〇COCH(R1)CH2S(R2)CO〇H)n (I) (wherein R1 represents a hydrogen atom or a methyl group, r2 represents a ketone group having a carbon number of 丨~12, X represents an organic group having a m:hn-valent carbon number of 3 to 6 Å, and m+n represents χ The number of turns, m represents an integer from 2 to 18, and η represents an integer from 1 to 3. R is a hydrogen atom or a sulfhydryl group. R2 is a hydrocarbon group having 1 to 12 carbon atoms. Representative examples of the suitable hydrocarbon group include an alkyl group having 1 to 6 carbon atoms and an aromatic group having 6 to 12 carbon atoms. Among these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 1 carbon atoms are more preferable. X represents an organic group having a m+n valence of from 3 to 60 carbon atoms. As suitable, trimethylolpropane and its derivatives, glycerin and its derivatives, isoprene 113376.doc 1378950 tetraol and its derivatives, ditrimethylolpropane and its derivatives, diisoprene A 111+11-valent group of a compound such as a tetraol and a derivative thereof, a polyisocyanate modified product of pentaerythritol, and a polyisocyanate modified body of diisodecyltetraol. Specific examples of X include, for example, a trivalent group represented by the following formula (derived from a thiol-based propyl group and a derivative thereof): [Chemical Formula 1]

(wherein R3 each independently represents an alkyl group of a carbon atom number i to 4, an alkyl group of CH2CH2〇CH2- or -CH2(CH3)CH-0-CH2 1 to 4); and R4 represents a carbon atom number represented by the following formula: The valence group (derived from the base of glycerol and its derivatives [2] ^

(wherein R5 is independently bonded directly (covalently bonded), represents -〇cH2CH2 or -〇CH(CH3)CH2-); the following formula represents a tetravalent group (derived from isopentanol and its derivatives) Foundation): [Chemical 3]

I13376.doc 1378950 (wherein R6 each independently represents a carbon atom number of ~4 alkyl, -CH2CH2OCH2- or -CH2(CH3)CH-〇-CH2-); the following formula represents a tetravalent group (derived from The base of ditrimethylolpropane and its derivatives): [Chemical 4]

(wherein R7 each independently represents an alkyl group having 1 to 4 carbon atoms, and R8 each independently represents an alkylene group having 1 to 4 carbon atoms, -CH2CH2〇Ch2- or -CH2(CH3)CH-0-CH2_ The following formula represents the valence group (derived from the base of diisopentaerythritol and its derivatives): [Chemical 5]

(wherein R each independently represents a stretching group having 1 to 4 carbon atoms, _CH2CH2〇CH2- or -CH2CH2CH2CH2COOCH2-) a hexavalent group represented by the following formula (a base of a polyisocyanate modified substance derived from pentaerythritol) ): 113376.doc 1378950 [Chem. 6]

(wherein R10 each independently represents an alkylene group having an anti-atom number of 1 to 4 and an aliphatic or aromatic hydrocarbon group having a number of atoms of 6 to 12;

The 10-valent group represented by the following formula (source white-V green from the base of polyisocyanate ruthenium of isoamyltetraol): [Chemical 7] 12 R12 〇12. Η ί3 Η ^ch2och2—^h2〒-rL¥ Ch4-

(wherein R12 independently represents an alkylene group having a carbon number of i to 4, and an Rn table

An aliphatic or aromatic hydrocarbon group having 6 to 12 carbon atoms). Among these, 'based on a group derived from trimethylolpropane and a derivative thereof, a group derived from isopentaerythritol and a derivative thereof, and a group derived from diisopentaerythritol and a derivative thereof are preferred. 0 m indicates the number of bonds to XiH2C = c(Ri)c〇〇_ base. m is an integer of 2 to 18, preferably an integer of 3 to 10. η represents a bond of X to 0 (: 〇 (: Η (Ι^) (: Η 2 δ (Ι 12) (: ΟΟΗ base number. η is an integer of 1 to 3, preferably 1 or 2. The compound containing a carboxyl group represented by I) can be easily prepared, for example, by the following method: 〇113376.doc 1378950, etc., that is, after acrylating the compound acrylic acid m which is imparted with an organic group represented by X, The compound obtained by adding the compound of the organic compound to the obtained compound is modified with a polyisocyanate compound, and the obtained compound is acylated with a C: acid compound having a hydroxyl group. Thereafter, a method of adding a thiolated compound to the obtained compound; a compound imparting an organic group represented by X with acrylic acid

t. A method of adding a mercapto compound to a compound obtained after the acidification of the polyisocyanate compound by acidification.

Examples of the compound which imparts an organic group represented by X include trimethylolpropane, an ethylene oxide adduct of trimethylolpropane, and a trioxindole: a propylene oxide propylene compound adduct of propylene oxide. , ternary methyl methacrylate (4) adducts, etc., trimethoprim and its derivatives; glycerol, glycerol, ethylene oxide adduct, glycerol propylene oxide adduct, glycerin Ester adducts, polyglycerols, ethylene oxide adducts of polyglycerols, propylene oxide adducts of polyglycerol, glycerol adducts of polyglycerol, and the like; isovalerol, Ethylene oxide adduct of isovaerythritol, propylene oxide adduct of isobaerythritol, caprolactone adduct of pentaerythritol, and the like; and bishydroxyl Ethylene oxide adduct of propane, ditrihydroxydecylpropane, propylene oxide adduct of di-dimethylmethylpropane, di-hydroxyl addition of di-trimethylolpropane-containing vinegar adduct Methylpropane and its derivatives; diisopentyl alcohol, diisodecyl alcohol ethylene oxide adduct, diisopentyl alcohol propylene oxide adduct, diisopentyl alcohol Ester adducts of dipentaerythritol and derivatives thereof; and the above-mentioned pentaerythritol and dipentaerythritol the modified polyisocyanate and the like. 113376.doc As the mercapto compound, for example, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-decyl benzoic acid, 2-sulfenylnicotinic acid, mercapto succinic acid, or the like can be mentioned. Examples of the polyisocyanate compound include: 2, indole diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, or , m- or p-)diphenylene diisocyanate, (ortho- or m-)-hydrogenated xylene diisocyanate, fluorenylene bis(cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, ring Hexane·1,3-diiminoguanidine diisocyanate, cyclohexane methylene diisocyanate, 1,5-naphthalene diisocyanate, etc., such polyisophthalic acid vinegar compounds may be used in one type or may be combined. Two or more types are used. The following describes a method of adding a compound which is obtained by adding an organic group represented by X to a compound obtained by adding a compound to the obtained compound. In the above method, a compound (hereinafter, referred to as an acrylated compound) obtained by acrylating a compound having an organic group represented by X in advance is used as a starting material instead of a compound having an organic group represented by X. The starting material is used. In the case where the acrylated compound is added to the mercapto compound, the amount of the mercapto compound is preferably from 1 to 30 parts by weight, based on 100 parts by weight of the acrylated compound, and more preferably from 1 to 30 parts by weight. The reaction of adding an acrylate compound to a mercapto compound may be carried out without a solvent, but if necessary, it may be ethyl acetate, butyl acetate, methoxypropyl acrylate, methyl methoxypropionate or ethoxylate. An ester-based organic solvent such as ethyl propionate, a ketone-based organic solvent such as acetophenone or cyclohexanone, diisopropyl ether, an ether organic solvent such as h H3376.doc.12-^78950 methoxylyl (diglyme), toluene It is carried out in an organic solvent such as an aromatic organic solvent such as xylene or benzene oxyphenol. Further, at the time of the reaction, a catalyst such as a phosphorus compound such as triphenylphosphine, an amine such as triethylamine, pyridine, Ν'Ν•dimethylbenzylamine or a quaternary salt thereof may be used. The amount of the catalyst is usually relative to the sulfhydryl compound i mole, which is preferably about 2% by mole. Further, the reaction temperature is usually 40 to 1 Torr (about TC is preferred. The carboxyl group-containing compound of the invention may be used after the refining of the compound containing a carboxyl group. The photosensitive resin composition of the present invention contains the above-mentioned compound containing a carboxyl group: in the photosensitive resin composition. The content of the compound containing a carboxyl group is preferably from 1 to 50% by weight, preferably from 2 to 40% by weight, from the viewpoints of photocurability, viscosity, chemical resistance and developability. In the composition, an organic solvent may be used as needed, and examples of the organic solvent include ethyl acetate, acetic acid, methoxypropyl acetate, methoxypropyl propionate, and ethoxylate. A vinegar-based organic solvent such as ethyl acetoacetate, an organic solvent such as methyl ethyl ketone or cyclohexanthene, an ether-based organic solvent such as isopropyl ether or diglyme, or an aromatic organic compound such as toluene or xylene. Solvent, etc., but the invention is not The organic solvent f is adjusted to have a total amount of 100% by weight based on the residue containing the compound and the additive to be added as needed. (3) In the photosensitive resin composition of the present invention, 'according to the need An additive such as a plasticizer, a sputum, a scented scented foaming agent, or a coloring agent may be added in an appropriate amount. As a method of applying the photosensitive resin composition of the present invention to a substrate, H3376.doc -13 For example, the spraying method, the roll coating method, the dipping method, and the like are exemplified, but the present invention is not limited to the examples. The substrate to which the photosensitive resin composition of the present invention can be applied is exemplified by - Metal base materials such as iron, copper, and stainless steel, glass base materials, epoxy resin, tantalum base materials, acrylic resin base materials, polycarbonate base materials, and polyester base materials, etc. However, the present invention is not limited to the examples. The shape of the substrate is not particularly limited, and may be any shape as long as it is used. The coated photosensitive resin composition of the present invention is coated. Thick film Although it is not possible to determine the degree depending on the use, it is usually about 0.1 to 50 μm. The photosensitive resin composition of the present invention has good photocurability and is sensitized by the present invention. The film formed of the resin composition has a property of being difficult to remain viscous and having excellent alkali solubility. EXAMPLES Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples. Example 1 In a four-necked flask of 1 L capacity, 298 g of trishydroxylpropane triacrylate obtained by acidifying trimethylolpropane, 31 g of thioglycolic acid, and N, N were placed. 1 g of benzylamine and 6 g of 4-decyloxyphenol oxime. The reaction was carried out at a temperature of 50 to 60 ° C for 4 hours to obtain an oily substance. A mixture of dihydroxydecyl propane triacrylate and thioglycolic acid, And the obtained oil is obtained by gel permeation chromatography, T〇s〇h (shared company 113376.doc U78950), HLC-8120 (column: SUPER-H 2500/2 linkage, detector .UV) measurement. The results of a mixture of tris-fluorenyl-triacrylates are disclosed in Figure 1, and the results of the obtained oils are disclosed in Figure 2. From the result shown in Fig. 2, as compared with Fig. 1, since the peak of thioglycolic acid disappeared, it was confirmed that the obtained oily substance was obtained by the addition of thioglycolic acid and the molecular weight of trimethylolpropane triacrylate. Further, the acid value of the oil obtained was investigated and its acid value was 48 mgKOH/g. Thereafter, the obtained oil was refined by cerium oxide gel column chromatography (developing solution: η-hexyl-ethyl acetate (capacity ratio: 7:3)), and the solvent of the obtained separation liquid was dried. After that, a transparent viscous body was obtained in a yield of 2% by weight. The 1H-NMR, infrared absorption spectrum, mass analysis and elemental analysis of the transparent adhesive body were carried out. The measurement methods and results are as follows. [Nuclear magnetic resonance dH-NMR spectrum] was measured by Nippon Electronics Co., Ltd., JNM_AL3 (condition: 3 〇〇 MHz, internal standard: TMS, solvent: heavy gas imitation (CDC 丨 3)). The results are disclosed in Figure 3. [Infrared absorption (IR) spectrum] FTIR_42〇〇 (condition: liquid film method (chlorinated steel plate)), manufactured by Shimadzu Corporation. The results are disclosed in Figure 4. [Quality analysis] Measured by _5〇〇〇 by Shimadzu Corporation and GC-MS. The result 'quality is 389 (m/z). ' [Elemental analysis] The sound value (C丨7H24〇8S): C52.6%, H6.2%, S8.30/. 113376.doc -15 Measured value: C53.8% ' H6.6%, S6.30/. From the above results, it was confirmed that the obtained transparent viscous system is a compound having a carboxyl group in the formula (I), wherein R1 is a hydrogen atom, R2 is a fluorenylene group, X is a trihydroxymethylpropanyl group, m.2, and η is 1. . Example 2 582 g of diisoamyltetraol hexaacrylate, 53 g of 3-mercaptopropionic acid, ruthenium, Ν-dimethylbenzylamine 1 g, and 4-methoxyl were placed in a 4-L flask. The base benzene age 0.6 g ' was reacted at a temperature of 50 to 60 ° C for 6 hours to obtain an oil. The oil obtained was examined by gel permeation chromatography. As a result, it was confirmed that the peak of the prosthetic acid disappeared and the diisopentyl alcohol hexaacrylate was polymerized by the addition of mercaptopropionic acid. The acid value of the oil was investigated and found to be 44 mgKOH/g. Example 3 Into a four-capacity four-necked flask, 360 g of isoamyltetraol tetraacrylate, 77 g of o-decyl benzoic acid, N,N-dimethylbenzylamine, and 4-methoxyphenol were placed. 0.6 g, the reaction was carried out at a temperature of 50 to 60 ° C for 6 hours to obtain an oil. The oil obtained was examined by gel permeation chromatography, and it was confirmed that the peak of the vortex benzoic acid disappeared, and the addition of decyl benzoic acid was used to quantify the polymer. The acid value of the oily substance was investigated and found to be 64 mgKOH/g. Subsequently, as the oily substance obtained in each of the examples and the physical properties of the compound used as a raw material, the viscosity, the refractive index and the alkali solubility were based on the following Method # estimate. The crusting is disclosed in Table 1. 113376.doc -16 - 1378950 [Viscosity] The viscosity at 25 ° C was measured using an E-type viscometer. [Refractive index] It was measured using an Abbe refractometer [manufactured by ATAGO Co., Ltd., product number: MODEL NAR-3T]. [Solubility] In 10 g of the epoxy acrylate resin obtained in the following Production Example 1, 6 g of an oily substance to be investigated for alkali solubility was mixed, and the mixture was diluted with a carbitol acetate to a solid form. 10% solution as a test solution. The turbidity of 1 g of the test solution dissolved in 100 g of a 1% sodium carbonate aqueous solution was measured using a turbidity meter [manufactured by HACH Co., Ltd., product number: MODEL 1890]. [Table 1] Example No. Property 25 ° C Viscosity (mPa.S) Refractive Index at 25 ° C Solubility (turbidity: NTU) 1 480 1.49 4 2 38000 1.50 74 3 5500 1.51 7 Trihydroxydecylpropane Triacrylate 80 1.48 41 Diisopentaerythritol hexaacetic acid vinegar 6500 1.49 200 or more pentaerythritol tetraacrylate 1100 1.48 55 From the results disclosed in Table 1, it is known that the oil obtained in each example (containing Each of the carboxyl group compounds has a higher viscosity than the raw material compound, a refractive index of about 1.5, and an excellent alkali solubility. Production Example 1 (Preparation of epoxy acrylate resin) 113376.doc 1378950 A cresol novolac epoxy resin was prepared in a four-necked flask of 1 L capacity [manufactured by Tohto Kasei Co., Ltd., product number: YDCN-704] 210 g 72 g of acrylic acid, 220 g of carbitol acetate, 0.75 g of 1,4-benzoquinone and 0.75 g of triethylmethylammonium chloride are allowed to be 8 〇 to 9 〇. The temperature of the crucible reacted for 14 hours. The acid value of the obtained reaction mixture was 1 mgKOH/g. To the reaction mixture, 6 〇 g of tetrahydrophthalic anhydride was placed, and the mixture was reacted at a temperature of 80 to 90 ° C for 6 hours to obtain an epoxy acrylate resin. The acid value when converting the epoxy acrylate acid to the solid content of the resin was Μ mgKOH/g. Example 4 12 g of the epoxy acrylate resin obtained in Production Example 1, 60 g of the oil obtained in Example 2, and 12 g of a photoinitiator (trade name: IRGACURE 907, manufactured by CibaGEIGY Co., Ltd.) were mixed. A photosensitive resin composition was obtained. Comparative Example 1 12 g of an epoxy acrylate resin i 〇〇g, diisopentaerythritol hexaacrylate, and a photoinitiator (manufactured by CIBAGEIGY Co., Ltd., IRGACURE 907) obtained in Production Example 1 were mixed. Photosensitive resin composition. Subsequently, the photosensitive resin composition obtained in Example 4 and Comparative Example was applied to a stainless steel plate (SUS3〇4) with a coating bar (coating bar No. 1), and then at a temperature of 80 ° C. The viscosity and the photocurability of the physical properties of the film to be formed were investigated by the following methods. These results are disclosed in Table 1. [Viscosity] The adhesion of the formed film will be investigated by finger touch, based on the following evaluation basis 113376.doc 10 1378950 Quasi-assessment [Evaluation Criteria] 〇: no viscous (the film is not adhered to the finger) x: viscous (film) Adhesive to the finger) [Photocuring property] The formed film is irradiated with an ultraviolet film (light source: 2 KW high pressure mercury lamp (8 〇 W/cm), distance from the light source to the film: 3 〇 cm), and one drop of acetone is dropped on the film. The amount of ultraviolet light required for dissolution and swelling due to acetone. Further, the smaller the amount of ultraviolet rays, the better the photocurability. [Example 2] Comparative Example No. Physical Viscosity Photocuring [Amount of Irradiation of Ultraviolet Light (mJ)] Example 4 〇70 Comparative Example 1 X 70 As a result of the absence of Table 2, it was found that Example 4 was obtained. The photosensitive resin composition maintains the same degree of photocurability as compared with the photosensitive resin composition obtained in the comparative example, and the adhesion is difficult to remain. Industrial Applicability The slow-setting compound of the present invention and the photosensitive resin composition using the same can be used for a wide range of applications such as paints, inks, adhesives, and insulating materials. BRIEF DESCRIPTION OF THE DRAWINGS The circle 1 is shown in Trimethylolpropane triacrylate used in Example 1. 13376.doc -19. 1378950 Gel permeation chromatography. Fig. 2 is a graph showing the results of measurement by gel permeation chromatography of the oily substance (the compound containing a carboxyl group) obtained in Example 1. Fig. 3 is a view showing the ^-NMR spectrum of the transparent viscous body obtained in Example 1. Figure 4 is a graph showing the infrared absorption (IR) spectrum of the transparent viscous body obtained in Example 1.

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Claims (1)

1378950 X. Patent application scope: 1 · A compound containing a carboxyl group which is represented by the formula (I): (H2C=C(R1)COO)mX-(OCOCH(R,)CH2S(R2)CO〇H)„ (I) (wherein R1 represents a hydrogen atom or a methyl group, 'R2 represents a nitrogen atom of a carbon number, X represents an organic group having a m+n valence of 3 to 60 carbon atoms, and m+n represents a valence of x, m represents an integer of 2 to 18, and η represents an integer of 1 to 3.) 2. The compound containing a carboxyl group of claim 1, wherein X is selected from the group consisting of m+n valence of a compound of the group consisting of Namely: trimethylolpropane and its derivatives, glycerin and its derivatives, pentaerythritol and its derivatives, ditrihydroxydecylpropane and its derivatives, diisopentaerythritol and its derivatives, isovaler A polyisocyanate modified body of tetraol and a polyisocyanate modified body of diisopentaerythritol. A photosensitive resin composition comprising a compound containing a carboxyl group of the claim or the like. 113376.doc