JP2505541B2 - Photopolymerization catalyst composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention provides a novel photopolymerization catalyst composition capable of obtaining increased photosensitivity when added as a component of the photopolymerizable composition. Regarding

(Prior art and its problems) Photopolymerizable compositions, that is, compositions that generate active species such as radicals by light irradiation to induce chemical reactions such as polymerization and crosslinking are paints, printing inks, photoresists, and adhesives. It is used in applications such as agents and dental composite resins.

In any of the applications described above, increasing the polymerization rate of the photopolymerizable composition, that is, increasing the photosensitivity of the photopolymerizable composition can shorten the exposure time by active light and improve the work efficiency. Therefore, it is industrially beneficial. Therefore, conventionally, researches have been mainly conducted to develop photoinitiators exclusively.

For example, a method of adding various photoinitiators to a photopolymerizable composition containing an ethylenically unsaturated compound has been performed. Examples of these photoinitiators include polynuclear quinones such as 2-ethylanthraquinone and 2-t-butylanthraquinone, aromatic ketones such as benzophenone, diazo compounds such as azobisisobutyronitrile, benzoin methyl ether and benzoin ethyl ether. Benzoin derivatives and the like.

However, the photopolymerizable composition obtained by using these photoinitiators does not necessarily have sufficient photosensitivity, and various photosensitizers may be combined with the above-mentioned photoinitiators to further improve photosensitivity. Are being implemented. As a combination of these photoinitiators and sensitizers, for example, a system of camphorquinone or benzophenone and 4,4 '-(dimethylamino) benzophenone is known.

In addition, a method of increasing the photosensitivity by combining the above-mentioned photoinitiator and a photoinitiator aid is also performed. Examples of combinations of these photoinitiators and photoinitiator aids include benzophenone or various aminophenyl ketones, active methylene compounds such as N-phenylglycine and N- (P-nitrophenyl) glycine, ethanolamine, and diethanolamine. And the like, or a combination of benzophenone or various aminophenyl ketones with a 2,4,5-triarylimidazole dimer, and the like.

However, in the method of increasing the photosensitivity of the photopolymerizable composition in the above-mentioned prior art, sufficient photosensitivity is not always obtained, or even when sufficient photosensitivity is obtained, sufficient storage stability is obtained. There is a problem that it does not exist or causes discoloration of the copper surface when it is used for manufacturing a printed circuit board.

(Means for Solving the Problem) In order to improve such conventional problems, as a result of earnest research, we have found a photopolymerizable composition having sufficient photosensitivity and excellent storage stability. The inventors have found the photopolymerization catalyst composition necessary for obtaining the same and have completed the present invention.

That is, the present invention includes (a) the general formula (I) (However, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms and have 1 to 10 carbon atoms.
15 alkyl group, cycloalkyl group, phenyl group, naphthyl group, C1-15 alkoxy group, C1-15 hydroxyalkyl group, C1-15 alkoxyalkyl group, C1-15 Alkylamino group, carbon number 1
The same or different groups selected from 15 alkyl esterified carboxyl groups, amino groups, hydroxy groups, halogen atoms, nitro groups and cyano groups are shown. 100 parts by weight of 2-phenyl-1,3-indandione or a derivative thereof represented by the formula (b), (b) 100 to 10,000 parts by weight of benzophenone, and (c) the general formula (II). (In the formula, R ′ and R ″ represent the same or different groups which are alkyl groups having 1 to 3 carbon atoms.) A photopolymerization catalyst composition comprising 5 to 1000 parts by weight of alkylaminobenzophenone. .

The compound represented by the general formula (I) used in the present invention (hereinafter, simply referred to as an indadione compound) acts as a photoinitiator aid, and particularly, the above-mentioned benzophenone and the alkylaminobenzophenone of the general formula (II). When combined with the above, a photopolymerization catalyst composition having excellent storage stability and increased photosensitivity can be obtained.

The indadione compound is represented by the above formula (I), and in the formula (I), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a cycloalkyl group. , A phenyl group, a naphthyl group, an alkoxy group having 1 to 15 carbon atoms,
C1-C15 hydroxyalkyl group, C1-C15 alkoxyalkyl group, C1-C15 alkylamino group, C1-C15 alkyl esterified carboxyl group, amino group, hydroxy group, halogen atom The same or different groups selected from a nitro group and a cyano group are shown. Further, these indandione compounds can be used alone or as a mixture of two or more kinds.

The indandione compound is derived from, for example, phthalide. For example, D described in J. Org. Chem., 26 , 3580 (1961)
Using the ieckmann reaction, phthalide is reacted with benzaldehyde or a derivative thereof in the presence of sodium alcoholate, for example, ethyl propionate is used as a solvent at 50 to 100 ° C. for 1 to 5 hours to obtain the desired indadione compound.

Preferred compounds include 2-phenyl-1,3-indandione, 2- (o-methylphenyl) -1,3-indandione, 2- (m-normalhexylphenyl)-
1,3-indandione, 2- (p-cyclohexylphenyl) -1,3-indandione, 2- (p-phenylphenyl) -1,3-indandione, 2- (p-naphthylphenyl) -1, 3-indandione, 2- (p-methoxyphenyl) -1,3-indandione, 2- (p-normaloctylphenyl) -1,3-indandione, 2-
(M-Hydroxymethylphenyl) -1,3-indandione, 2-p- (2-methoxyethylphenyl) -1,3
-Indandione, 2- (p-dimethylaminophenyl) -1,3-indandione, 2- (p-dihexylaminophenyl) -1,3-indandione, 2- (p-carboxyphenyl) -1,3 -Indandione, methyl ester, 2- (p-carboxyphenyl) -1,3-indandione, dodecanyl ester, 2- (o-aminophenyl) -1,3-indandione, 2 (p-hydroxyphenyl) -1,3-indandione, 2- (p-chlorophenyl) -1,3-indandione, 2- (m-bromophenyl) -1,3-indandione, 2- (o-fluorophenyl) -1, There are 3-indandione, 2- (p-nitrophenyl) -1,3-indandione, 2- (p-cyanophenyl) -1,3-indandione and the like.

Among the above-mentioned indandione compounds, 2-phenyl-1,3-indandione compound having particularly high sensitivity, and at least a part of the phenyl ring of the compound have an alkyl group having 1 to 15 carbon atoms and a carbon number of Examples thereof include indione compounds substituted with an alkoxy group having 1 to 15 atoms, a halogen atom, or an alkyl esterified carboxyl group having 1 to 15 carbon atoms.

The benzophenone of the present invention is an essential component used in combination with the indandione compound and the alkylaminobenzophenone, and when these three components are used in combination, a significantly increased photosensitivity is obtained.

Further, the general formula (II) which is another essential component of the present invention
The alkylaminobenzophenone represented by
For example, p, p'-dimethylaminobenzophenone (abbreviation:
Michler's ketone), p, p′-diethylaminobenzophenone and the like, and these can be used alone or as a mixture of two or more kinds.

The composition ratio of the indandione compound, benzophenone, and alkylaminobenzophenone in the photopolymerization catalyst composition of the present invention is indandione compound 100.
Benzophenone is preferably 100 to 10,000 parts by weight, and more preferably 1000 to 5000 parts by weight, based on parts by weight. If the amount of benzophenone added is 100 parts by weight or less, the increase in photosensitivity is slight and sufficient photosensitivity for practical use cannot be obtained.
On the other hand, when the amount is 10,000 parts by weight or more, the effect reaches saturation and no further increase in photosensitivity is observed. Alkylaminobenzophenone is also used in the indandione compound 10
The amount is 5 to 1000 parts by weight, preferably 10 to 50 parts by weight, based on 0 parts by weight. If it is 5 parts by weight or less, the increase in photosensitivity is slight, and if it is 1000 parts by weight or more, the effect is saturated and there is no economic advantage.

The photopolymerization catalyst composition of the present invention comprises a monomer having at least one ethylenically unsaturated group known as one of the components of the photopolymerizable composition, and a thermoplastic polymer if necessary. Can be used in combination. In this case, the photopolymerization catalyst composition of the present invention is preferably added to the photopolymerizable composition in an amount of 0.01 to 15% by weight, preferably 0.1 to 10% by weight. If the amount of the catalyst composition added is less than 0.01% by weight, sufficient photosensitivity cannot be obtained. If it is more than 15% by weight, the storage stability of the photopolymerizable composition is lowered, which is not preferable.

Generally, a copolymer of an unsaturated carboxylic acid and an unsaturated carboxylic acid ester can be preferably used as the thermoplastic polymer. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid and maleic acid. Examples of the unsaturated carboxylic acid ester include methyl, ethyl, butyl, 2-ethylhexyl ester of acrylic acid or methacrylic acid. In addition, as the thermoplastic polymer, unsaturated carboxylic acid,
Homopolymer of unsaturated carboxylic acid ester, styrene-
Alternate copolymers such as maleic anhydride copolymers, polycondensates of terephthalic acid, isophthalic acid and sepacic acid, and cellulosic polymers can also be used.

The thermoplastic polymer is usually used in the composition for photopolymerization in an amount of 0 to 80% by weight, if necessary. If it is more than 80% by weight, the other components are relatively small and the photosensitivity is lowered.
In some cases, when the photopolymerizable composition is applied, the flexibility of the coating layer is significantly reduced, and the coating layer may be broken during use, which is not preferable.

Further, specifically exemplifying a monomer that can be generally used as a monomer having at least one ethylenically unsaturated group, an alkyl ester of acrylic acid or methacrylic acid,
For example, methyl methacrylate, ethyl methacrylate, -n-butyl methacrylate, 2-ethylhexyl methacrylate; unsaturated carboxylic acid esters of polyhydric alcohols, such as triethylene glycol diacrylate, trimethylol methane diacrylate, trimethylol propane. Triacrylate, tetramethylolmethane tetraacrylate; unsaturated carboxylic acid ester of glycidyl group-containing compound, for example, trimethylolmethane diglycidyl ether diacrylate, trimethylolpropane triglycidyl ether triacrylate; acrylic acid or methacrylic acid ester of bisphenol A derivative , For example, 2,2bis [4- (methacryloxy-diethoxy) phenyl] propane, 2,2bis [4-methacryloxy-polyethoxy) phenyl Propane or the like is used. still,
These monomers are used alone or as a mixture of two or more. The composition ratio of the monomer in the photopolymerizable composition is 10
˜90 wt%, preferably 20-60 wt%. 10% by weight
When it is below, the curing reaction after exposure becomes insufficient, which is not preferable. Further, when it is 90% by weight or more, the addition amount of other components becomes relatively small and sufficient photosensitivity cannot be obtained, and in some cases, the fluidity of the photopolymerizable composition becomes too large, and thus the coating is difficult. And it becomes impossible to fix.

The photopolymerizable composition obtained by adding the photopolymerization catalyst composition of the present invention contains various known thermosetting polymers, fillers such as fillers, or p-methoxy, in addition to the components described above. Thermal polymerization inhibitors such as phenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine and t-butylcatechol, or dyes or pigments such as crystal violet, Victoria blue, arachitogtan and methyl orange may be added.

Further, in addition to the above components, known additives such as a plasticizer and an adhesion promoter, or a combination of a leuco dye and a halogen compound may be added so that the exposed area is colored.

The photopolymerizable composition obtained by adding the catalyst composition of the present invention is a solvent that dissolves the above components, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl alcohol, tetrahydrofuran, toluene, methyl cellosolve, and ethyl cellosolve. A uniform solution can be obtained by mixing and dissolving single or a mixture.

The light source required for photopolymerization is not particularly limited and known ones can be used, and generally, a wavelength of 300 to 450 is preferable.
It emits nm light. Specific examples include mercury vapor arc, carbon arc, and xenon arc.

(Effect of the Invention) The photopolymerization catalyst composition of the present invention provides a photopolymerizable composition having sufficient photosensitivity and excellent storage stability. Further, when the photopolymerizable composition obtained by adding the photopolymerization catalyst composition of the present invention, for example, when used in the production of printed circuit boards, suppress the discoloration of the copper substrate surface, photo excellent in fine line adhesion It can be used as a resist.

(Examples) Hereinafter, the present invention will be described by way of examples by taking the case of application as a photoresist as an example, but the present invention is not limited by these examples.

Reference Example (a) Synthesis of 2-phenyl-1,3-indandione Phthalide 0.2 mol, benzaldehyde 0.2 mol, sodium methylate 0.6 mol, ethyl propionate 100 ml 50
Charge in a 0 ml three-necked flask and dissolve evenly, then reflux at 65 ° C for 2 hours. After cooling to room temperature, it is filtered to obtain crystals. The crystals were recrystallized with acetone. The final yield was 70.1%. The product was confirmed by ¹ H-NMR.

(B) Synthesis of 2-phenyl-1,3-indandione derivatives Various 2-phenyl-1,3-indandione derivatives used in the present invention are the above-mentioned (a) Method for synthesizing 2-phenyl-1,3-indandione. In the same manner, various benzaldehyde derivatives were used instead of benzaldehyde. As the recrystallization solvent, an appropriate one was selected from methanol, ethanol, acetone and methyl ethyl ketone and used.

Examples 1-6 and Comparative Examples 1-10 The following photopolymerizable compositions were prepared. That is, first of all, acrylic copolymer (46% ethyl acrylate, 37%
Containing ethyl methacrylate and 15% acrylic acid,
It has a logarithmic viscosity of 0.458 at 30 ° C in methyl ethyl ketone) 70 parts by weight triethylene glycol dimethacrylate 20 parts by weight Brilliant Green Dye (CI # 42040) 0.04 parts by weight Leuco Crystal Violet 0.5 parts by weight Tetrabromomethane ... 1.0 part by weight Methyl ethyl ketone ... 300 parts by weight are uniformly dissolved to obtain a solution A. Next, various compounds having the addition ratios shown in Table 1 were added to this solution A to obtain a photopolymerizable composition of the present invention or a comparative example.

The performance of this photopolymerizable composition was evaluated by the following methods. First, under the illumination of a yellow fluorescent lamp, it was applied using a doctor blade on a polyester film having a thickness of 25μ, air-dried for 30 minutes, and then dried in an oven at 80 ° C for 5 minutes to form a dry film. . Dry film thickness is 38μ
Met. This dry film was applied to a copper clad laminate whose surface was polished with a hot roller laminator at 130 ℃, 1m / min.
Laminated under the conditions. After leaving this for 10 minutes to cool to room temperature, step tablets (trademark "gray scale", optical density step 0.15, minimum optical density 0.05, maximum optical density 3.05, 21 steps) are adhered on the polyester film, It was exposed with a 3kW ultra-high pressure mercury lamp. The exposure amount is
It was measured by "Ultraviolet illuminometer UV-M01" manufactured by Oak Manufacturing Co., Ltd. using a sensor having a spectral sensitivity maximum at 350 nm. When dimming, one to ten 0.3 mm thick PZT films were placed on the step tablet. After leaving it as a hold time for 10 minutes, it was developed with a 1% aqueous sodium carbonate solution at 30 ° C.
Regarding the sensitivity, the exposure amount required for the Stoffer step tablet (21 steps) to show 9 was shown in mJ / cm ² .
Tables 1 and 2 show a comparison of sensitivity.

Examples 7 to 36 Various 2-phenyl-1,3 synthesized by the method of Reference Example (b) instead of 2-phenyl-1,3-indandione
-The same procedure as in Example 1 was carried out except that an indandione derivative was used. Table 2 shows the types of 2-phenyl-1,3-indandione derivatives used and the results thereof. The benzophenone and the alkylaminobenzophenone, which are the essential combination components, and the amount ratio of them are the same as in Example 1, and are omitted.

Claims (1)

(57) [Claims] 1. (a) General formula (I) (However, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms and have 1 to 10 carbon atoms.
15 alkyl group, cycloalkyl group, phenyl group, naphthyl group, C1-15 alkoxy group, C1-15 hydroxyalkyl group, C1-15 alkoxyalkyl group, C1-15 Alkylamino group, carbon number 1
The same or different groups selected from 15 alkyl esterified carboxyl groups, amino groups, hydroxy groups, halogen atoms, nitro groups and cyano groups are shown. ) 100 parts by weight of 2-phenyl-1,3-indandione or a derivative thereof represented by the formula (b), 100 to 10,000 parts by weight of benzophenone, and (c) the general formula (II) (In the formula, R ′ and R ″ represent the same or different types of alkyl groups having 1 to 3 carbon atoms.) A photopolymerization catalyst composition comprising 5 to 1000 parts by weight of alkylaminobenzophenone.