JPH02289602A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To provide the subject new composition comprising an ethylenic unsaturated group-containing high boiling point compound, a thermoplastic organic polymer and an acridine compound photopolymerization initiator in a specific ratio, having enhanced photosensitivity. CONSTITUTION:The objective composition comprises (A) 100 pts.wt. of an ethylenic unsaturated group-containing compound [e.g. tetraethylene glycol di(meth)acrylate], (B) 0-400 pts.wt. of a thermoplastic organic polymer [e.g. a copolymer of (meth)acrylic acid alkyl ester and (meth)acrylic acid] and (C) 0.01-10 pts.wt. of a photopolymerization initiator consisting of an acridine compound of the formula [R1 is 2-20C hydrocarbon, -(R2O)n-R2 (R2 is 2-4C alkylene; n is 1-10)].

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photopolymerizable composition. For more details. The present invention relates to a novel photopolymerizable composition with increased photosensitivity.

(Prior Art) Increasing the polymerization rate of a photopolymerizable composition, that is, increasing the photosensitivity of the photopolymerizable composition, is beneficial in that the exposure time of active light can be shortened. Conventional. Various methods have been used.

For example, in photopolymerizable compositions containing ethylenically unsaturated group-containing compounds to increase photosensitivity. Methods of adding photoinitiators or sensitizers have been used. These photoinitiators or sensitizers include. 2-Ethylanthraquinone. Polynuclear quinones such as 2-t-butylanthraquinone.
Penzophenone. 4. Aromatic ketones such as 4'-bis(dimethylamino)penzo7enone. Benzoin methyl ether. Benzoin derivatives such as penzoin ethyl ether are used. however. The photosensitivity of conventional photopolymerizable compositions obtained using these photoinitiators or sensitizers has not always been sufficient.

Furthermore, in order to increase photosensitivity, a combination of aromatic ketones such as aminophenyl ketone and 2,4.5-doria J-imidazole dimer may be used (% Kosho 4
No. 8-38403, U.S. Pat.
No. 1936, US Pat. No. 877,853) are known.

Japanese Patent Publication No. 53-27605 discloses an acridine or phenazine compound that can contain a fused benzole ring. It is disclosed as a photoinitiator with high sensitivity and excellent storage stability, especially in the presence of oxygen. Unexamined Japanese Patent Publication 1987-
Publication No. 226002 κ discloses a combination of 9-phenylacridine and a thiol group-containing heterocyclic compound as a highly sensitive photoinitiator. Also, JP-A-60-16
No. 4739 discloses substituted 9-penzoylacridine as a highly sensitive photoinitiator.

However, even with these conventional compounds. None of these methods provided a photopolymerizable composition with satisfactory photosensitivity.

(Problems to be Solved by the Invention) An object of the present invention is to eliminate the drawbacks of the prior art and provide a novel photopolymerizable composition with increased photosensitivity.

(!!Means for solving the problem) The present inventors used an acridine compound having a specific heterocyclic aromatic group as a substituent as a photoinitiator. The present invention was achieved by discovering that the above object can be achieved by using the present invention in a composition containing a compound having an ethylenically unsaturated group.

The present invention is. (1) A compound having a boiling point of 100°C or higher at normal pressure and having at least one ethylenically unsaturated group
00 parts by weight (2) θ~400 parts by weight of a thermoplastic organic polymer and (3) a photoinitiator in a proportion of 0.01 to 10 parts by weight. The photoinitiator has the following general formula (Il
The present invention relates to a photopolymerizable composition K which is an acridine compound represented by:

(In the formula, s Rl is a hydrocarbon group having 2 to 20 carbon atoms or -←R20). R! - indicates m Rs is the number of carbon atoms 2
Indicates an alkylene group of ~4 * Indicates an integer of nidl to 1o. ) Used in the photopolymerizable composition of the present invention, at normal pressure 1
The compound component (1) having a boiling point of 00°C or higher and containing at least 11 ethylenically unsaturated groups is. For example, compounds obtained by adding α,β monounsaturated carboxylic acid to a polyhydric alcohol, such as tetraethylene glycol di(meth)acrylate (meaning methacrylate or acrylate, the same applies hereinafter), polyethylene glycol di(meth)acrylate (The number of ethylene groups is 2 to 1
4), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)azilylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)azilylate, polypropylene glycol di( For glycidyl group-containing compounds such as meth)acrylate (those with 2 to 14 propylene groups), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. Compounds obtained by addition of α,β monounsaturated carboxylic acids, such as trimethylolgloban triglycidyl ether triacrylate, bisphenol A
diglycidyl ether diacrylate, etc. Esterified products of polyhydric carboxylic acids, such as phthalic anhydride, and substances having hydroxyl groups and ethylenically unsaturated groups, such as β-hydroxyethyl (meth)acrylate, alkyl esters of acrylic acid or methacrylic acid, such as ) Acrylic acid methyl ester, (meth)acrylic acid ethyl ester. (meth)acrylic acid butyl ester, (meth)
Examples include acrylic acid 2-ethylhexyl ester. Furthermore, the components used in the photopolymerizable composition of the present invention (1)
) include compounds having at least one incyanate group, such as echatoluene diisocyanate, trimethylhexamethylene diisocyanate, di7enyl diisocyanate. Diphenylmethane diisocyanate}, 3.
3'-dimethyl. 44'-diphenyl diisocyanate, etc., and a compound having at least one hydroxyl group and at least one vinyl group, e.g. Examples include reaction products with β-hydroxy (meth)acrylate, vinyl alcohol, trimethylolpropane diacrylate, tetramethylolmethane (meth)acrylate, diethylene glycol mono(meth)acrylate, and the like.

As a thermoplastic organic polymer (component (2)). for example(
Copolymers of meth)acrylic acid (meaning methacrylic acid or acrylic acid; the same applies hereinafter) alkyl esters and (meth)acrylic acid, copolymers of (meth)acrylic acid alkyl esters, (meth)acrylic acid, and these. A copolymer with a vinyl monomer that can be used is used. Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid methyl ester. Examples include (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic a2-ethylhexyl ester, and the like.

In addition, (meth)acrylic acid alkyl esters and rubinyl monomers copolymerized with (meth)acrylic acid include (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylethyl ester, and (meth)acrylic acid diethyl ester. Ester, methacrylic acid glycidyl ester. 2,2.2-}Refluoroethyl (meth)acrylate, 2,2. &3-tetrafluoroprobil (
meth)acrylate acrylamide, diacetone acrylamide. Examples include styrene and vinyltoluene.

Also, as a thermoplastic organic polymer. Homopolymers of the above compounds can also be used, as well as copolyesters such as terephthalic acid. Polyesters of isophthalic acid and sebacic acid, etc. Also usable are copolymers of butadiene and acrylonitrile, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, and the like.

The blending amount of the thermoplastic organic polymer is 0 to 400 parts by weight. Preferably it is 20 to 250 parts by weight.

The use of thermoplastic organic polymers improves coating properties and the strength of the resulting cured product. If this amount is more than 400 parts by weight, the photosensitivity will decrease because the other components will be relatively small. Further, the weight average molecular weight of this thermoplastic organic polymer is preferably 10,000 or more from the viewpoint of the aforementioned coating properties and film strength.

As the photoinitiator (component (3)) of the present invention, an acridine compound represented by the above general formula (I) is used.
Examples of the hydrocarbon group having 2 to 20 carbon atoms represented by Rl include 1,2-ethylene, 1,2-propylene, 1,3-propylene. 2,2-dimethyl-1,3-
propylene. 1.2-Butylene. 1.4-butylene, hexamethylene. Octamethylene, decamethylene, dodecamethylene. 1.4-Cyclohexylene. p-cyclohexane dimethylene/, p-benzenedimethylene, 4.4'-
Isopropylidene bis(cyclohexylene). Examples include p-phenylene, 4,4'-isobropylidene bis(phenylene), and the like. t Nine, R! An alkylene group having 2 to 4 carbon atoms represented by Fi, 1,2-ethylene, 1,2-propylene, 1,3-brobylene, 1,2-
Butylene. Examples include 1,4-butylene.

Examples of the compound represented by the above general formula (1) include the following compounds No. 1 to No. 4, but Nlll,k
A compound of 2,N[l3 is particularly preferred from the viewpoint of sensitivity and the like.

Nlll Nα4 NIl2 3 The compound represented by the general formula (I) is, for example, β-(
acridin-9-yl)acrylic acid or its reactive derivatives such as alkali metal salts or monoesters
Glycols represented by -R, +-Of{ or X-R
It can be easily produced by reacting with a dihalide represented by tX (X represents a halogen atom).

β used as an intermediate to obtain the compounds of the present invention
-(acridin-9-yl)acrylic acid or its alkali metal salt. It is known that 9-(2-hydroxy-λλ3-trichloropropyl)acridine obtained by reacting 9-methylacridine with chloral can be easily produced by reacting with an alkali metal hydroxide such as potassium hydroxide. ing.

Also, F5 Research (Yiyao Gongye) No. 3, pages 8-11. (1984) describes that β-(acridin-9-yl)acrylic acid, its alkyl esters, and amide compounds are effective in the treatment of Japanese schistosomiasis; There is no mention of diester compounds of carboxylic acids, and no mention of the use of these compounds as photoinitiators. It does not imply the invention.

The compound represented by the general formula (I) of the present invention thus obtained can be used alone as a highly effective initiator, but
as needed. It can also be used in combination with other conventionally known photoinitiators.

The photoinitiator (component (3)) of the present invention comprises component (1) 1
0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. If it is less than 0.01 parts by weight, sufficient photosensitivity cannot be obtained and the photopolymerization will not progress sufficiently, and if it exceeds 10 parts by weight, the storage stability of the photopolymerizable composition will be low and it cannot be put to practical use.

The photoinitiator (component (3)) in the present invention may be used in combination of two or more types, or may be used in combination with various other organic amine compounds, organic sulfur compounds, etc.

Examples of these organic amine compounds include triethanolamine. Triinpropanolamine, methyldiethanolamine, octyldiethanolamine, octadecyldiethanolamine, dibutylethanolamine, dioctylethanolamine, diethanolaniline, diethanolamine, methylethanolamine, butylethanolamine, tetrahydroxyethylethylenediamine, tetrahydroxyethylhexamethylenediamine, triethylamine, Tributylamine. Dimethylaminopropylamine. Dimethylaniline, 4-dimethylaminotoluene. 4-diethylaminotoluene, 4
-dimethylaminocyanobenzene, 4-diethylaminocyanobenzene. 4-dimethylaminopromobenzene.
4-diethylaminobromobenzene, 4-dimethylaminonitrobenzene, 4-diethylaminonitrobenzene. 4-dimethylanoyl ester, fragrant alkyl ester, 4
-diethylaminobenzoic acid alkyl ester, 4-dimethylaminopyridine, 4-diethylaminopyridine 7,
4-pyrrolidinopyridine, phenylglycine. Diethylaniline, diethylamine. Examples include dioctylamine, tetramethylethylenediamine, Michler's ketone, and anthranilic acid.

Examples of organic sulfur compounds include 2-mercaptoimidazole, 2-mercaptooxazole, and 2-mercaptothiazole. 2-mercagutobenzimidazole, 2-mercaptopenzoxazole, 2-mercaptobenzothiazole. 6-chloro-2-mercaptobenzimitazole, 5-methylmercabut-1-7enyltetrazole, 6-methoxy-2-mercaptopenzimitazole. 2-mercaptonaphthoimidazole, 2-mercaptonaphthoxazole, 3-mercapto-1. 2. 4
-Triazole, etc.

Examples of the photopolymerizable composition of the present invention include p-methoxyphenol, hydroquino/birogallol, naphthylamine, and phenothiazine. A thermal polymerization inhibitor such as t-butylcatechol can be included.

The photopolymerizable composition of the present invention may also contain colorants such as dyes and pigments. As the coloring agent, for example, fuchsin, auramine base, crystal violet, Victoria Pier blue, malachite green, methyl orange, acid violet RRH, etc. are used.

Furthermore, the photopolymerizable composition of the present invention contains a plasticizer and an adhesion promoter. Known additives such as talc may be added, and a combination of a halogen compound such as carbon tetrabromide and an a-ico dye may be added so that the exposed area changes color.

The photopolymerizable composition of the present invention is prepared using a solvent that dissolves each of the above components, such as acetone, methyl ethyl keto/. Methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene ffl/, methyl alcohol. By dissolving and mixing with ethyl alcohol etc., it can be used as a solution photopolymerizable composition containing a solvent or
It is used as a solvent-free solution photopolymerizable composition in which other components are dissolved in the ethylenically unsaturated compound (component (1)) without using such a solvent.

These are the roll coater and curtain coater for each printing. It may be applied directly to a base material such as a copper plate by known means such as dipping. Further, once applied to a support such as a film, if it contains a solvent, it may be applied to a substrate after removing this solvent, and there are no particular restrictions on the method.

The photopolymerizable composition of the present invention is a photocurable paint. It can be used in various applications such as photocurable inks, photosensitive printing plates, photoresists, etc., and there are no particular restrictions on the applications. For example, when used as a printed wiring board photoresist. The solution-form photopolymerizable composition is applied to a base material such as a copper plate. If it contains a solvent, dry it and then expose it to active light. It can be used after being photocured. As described above, a solution photopolymerizable composition is applied onto a polyethylene terephthalate film, and if it contains a solvent, it is dried and then laminated onto a substrate.
It can be used after being photocured.

The active light source used for photocuring is: A material that emits light with a wavelength of 300 to 450 nm is used, and preferred examples include mercury vapor arc, carbon arc, and xenon arc.

(Effects of the Invention) The photopolymerizable composition of the present invention has high photosensitivity.

(Example) The present invention will be explained below with reference to Examples.

A synthesis example is shown below.

Synthesis Example 1 1.4-Butylenebis[β-(acridin-9-yl)
Synthesis of β-(acridin-9-yl)acrylic acid potassium salt 5
4G (0.188 mol) to N. Dispersed in N-dimelformamide 2009, where 1,4-dibromopta/20
9 (0.093 mol) was added, heated and stirred. The reaction mixture became a homogeneous solution at about 80°C.

After stirring at 100°C for 2 hours, the mixture was cooled to 50°C. After removing the precipitated potassium bromide, it was cooled to 15°C. The product precipitated out.

The product was filtered, washed with water, and then washed with 50 m/m of methanol. Drying under reduced pressure gave the product 41.69 (yield: 81) as a yellow powder with a melting point of 171-174°C.

The results of NMR analysis of the obtained product are as follows. I confirmed that it was the target object.

N! IJR (CDCIg solution.TMS standard) δ value: 1
．． 2-1.9 (4H.m.-CH2-)4
．． 2-4.5 (4H.t.-0-CH2-)6
．． 4 (2H. d. J=17Hz. -Co
-CH=CH-) 7.2 ~ 8.2 (16H, ms aromatic hydrogen) 8.5 (2H. d. J=17Hz.-
Co-CH=CH-) Further, the results of measuring the ultraviolet absorption spectrum and vector of the obtained compound are shown below.

λmax = 362 nm, g = 1.82 The same procedure as in Example 1 was carried out except that bromide was used. fusion a25
The title compound was synthesized as a yellow powder at 8-263°C.

NMR (DMSO-d' solution, TMS standard) δ value: 5
．． 2 (4H, s, -CHz-φ-CH2)6
．． 4 (2H, d. J=17Hz.-Co-
CH=CH-) 7.1-8.2 (20H.m, aromatic hydrogen)8
．． 5 (2H. d, J=17Hz.-Co-
CH=('J{-') Further, the results of measuring the ultraviolet absorption spectrum of the obtained compound are shown below.

λmax=362nm. #=1.6 5X 10'
Synthesis Example 3 Triethylene glycol bis[β-(acridine-9-
Methyl β-(acridin-9-yl)acrylate 139
(0.05 mol). Triethylene glycol 3,09 (
0.02 mol) and xylene aog, and stirred. 0.2 m/m of Tetrisobyl titanate was added.

140-141℃ while distilling off the methanol produced.
The mixture was stirred for 6 hours.

It was cooled to 80°C and 30m/ml of water was added. After a trace amount of insoluble matter was filtered off, 40 ml of xylene was added, washed with water, dried, and the solvent was removed.

The resulting reddish-brown liquid was purified using a silica gel column to obtain a highly viscous yellow liquid product.

NMR (CDCIs solution, HMDS standard) δ value: 3.
6-3.8 (8 H. m, -CHt-0-C'
Ht-)4.3~4.5 (4H.m.-CO
-0-CHz-)"' (2H.d, J=1
7Hz, -CO-CH=CH-) 7.1-8.2 (1 6H, m. aromatic hydrogen) 8
．． 2 (2H.d.J=17Hz, -C
O-CH=CH- 1 Further, the results of measuring the ultraviolet absorption spectrum of the obtained compound are shown below.

λ+max=360nm. #=1.48X10'neopentylglycol bis[β-(acridin-9-yl)
acrylate] (the compound marked with circle 4 above) was synthesized using neopentyl glycol in the same manner as the synthesis of compounds Il & I3.

Examples 1 and 2 Solution A was obtained by blending tetraethylene glycol diacrylate 4009, malachite green 2g, barium sulfate 1009, methyl alcohol 109 and dimethylformamide 30g. A solution of the photopolymerizable composition of the present invention was obtained by dissolving the photoinitiator in the amount shown in Table 1 in this solution AK (Examples 1 and 2).

Next, this solution was applied onto a copper plate using an applicator and dried in a hot air dryer at 100°C for 10 minutes. The coating thickness was approximately 20 μm. Next, this copper plate was passed 20 cm under a 7 kW high-pressure mercury lamp at a conveyor speed of 3 m/min. The number of passes until the finger tack on the surface disappeared was investigated. The results are shown in Table 1. It shows that the smaller the number of passes, the higher the photosensitivity. For comparison, a composition that does not use the photoinitiator used in the photopolymerizable composition of the present invention as a photoinitiator (Comparative Example 1, using penzophenone and Michler's ketone as a photoinitiator) was similarly evaluated for the number of passes until curing. Check out. The results are also shown in Table 1.

Table 1 The results shown in Table 1 show that the photopolymerizable composition of the present invention has high photosensitivity.

Examples 3 to 6 [Formulation] Heavy k part 2-mercabutobenzothiazole 0.12 Sample compound (see Table 2) 0.12 After thoroughly kneading the above formulation, a VC of 20 μm was prepared on a glass plate using a doctor knife. Apply it evenly to the thickness.9. Expose this glass plate to 50 mJ of light using a high-pressure mercury lamp.9.

From this coating. A No. 2 dumbbell test piece specified in JISK-7113 was taken and a tensile test was performed using an 8TM-H-500 testing machine (manufactured by Toyo Goldfin Co., Ltd.). 50%
The Young's modulus at the time of elongation was calculated, and the cured state of the coated material was investigated. The results are shown in Table 2.

The results shown in Table 2 show that the acridyl acryl A/acid xx ter compound of the present invention is more effective as a photoinitiator than the conventionally known 9-phenylacridine.

Examples 7 to 10 Methyl methacrylate/methacrylic acid/2-ethylhexyl acrylate (weight ratio 60/20/20) copolymer (weight average molecule t'=is 10,000) 529, tetraethylene glycol diacrylate 109, poly( P?5) Dimethacrylate of oxyethylated bisphenol A (BPE-10 manufactured by Shin-Nakamura Chemical Co., Ltd.) 309,
malachite green 0. 29, Hydroquinone 0.
19, Leuco Crystal Piolet}1.09. 0.59 g of carbon bromide, 109 g of toluene, 130 g of methyl cellosolve, 5 g of methyl alcohol, and 10 g of chloroform were blended to obtain 248.8 g of solution B (total nonvolatile content: 93.89). A photoinitiator was dissolved in this solution B in the proportions shown in Table 3 to obtain a solution of the photopolymerizable composition of the present invention.

Next, this solution was dried for about 5 minutes on a polyethylene terephthalate film having a thickness of 25 .mu.6 m using a KM-&ll cloth L, Zoo DEG C. hot air convection dryer to obtain a photopolymerizable element. The film thickness of the photopolymerizable composition after drying was 25 μm.

On the other hand, copper-clad laminates (MCL manufactured by Hitachi Chemical Co., Ltd.), which are glass epoxy materials laminated with steel foil (thickness 35 μm) on both sides, were used.
-E-61) The copper surface of The elements were laminated while being heated to 120°C.

Next, using a negative film, the substrate thus obtained was exposed to light at 40 mJ/cm' using a 3 kW high-pressure mercury lamp (manufactured by Oak Seisakusho ■, Phoenix-3000). At this time, in order to be able to evaluate the photosensitivity, we used a negative film that was made so that the amount of light transmission decreased step by step (the first step was an optical density of 0.05, and the optical density increased by 0.15 for each step). Step tablet) was used.

Next, remove the polyethylene terephthalate film,
The unexposed areas were removed by spraying 2 tons of aqueous sodium carbonate solution for 50 seconds at 30°C. Furthermore, the photosensitivity of the photopolymerizable composition was evaluated by measuring the number of step tablets in the photocured film formed on the copper-clad laminate. The results are shown in Table 3. The higher the number of steps on the step tablet, the higher the photosensitivity.

The results in Table 3 show that the photopolymerizable composition of the present invention has high photosensitivity.

(Effects of the Invention) The substituted acridine derivative of the present invention and the photopolymerizable composition containing the same can be suitably used in applications requiring high photosensitivity.

Agent: Patent Attorney Kunihiko Wakabayashi

Claims (1)

[Claims] 1. (1) 100 parts by weight of a compound having a boiling point of 100°C or higher at normal pressure and having at least one ethylenically unsaturated group (2) 0 parts by weight of a thermoplastic organic polymer 400 parts by weight and (3) a photoinitiator in a proportion of 0.01 to 10 parts by weight, the photoinitiator is expressed by the following general formula (
A photopolymerizable composition comprising an acridine compound represented by I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents a hydrocarbon group having 2 to 20 carbon atoms or -(R_2O)-_nR_2-, and R_2 represents an alkylene group having 2 to 4 carbon atoms. group, and n represents an integer of 1 to 10.) 2. In the general formula (I) of the photoinitiator, R_1 is 1,4
-The photopolymerizable composition according to claim 1, which is a butylene group. 3. The photopolymerizable composition according to claim 1, wherein R_1 in the general formula (I) of the photoinitiator is a p-xylylene group. 4. In the general formula (I) of the photoinitiator, R_1 is -C_
The photopolymerizable composition according to claim 1, which is 2H_4-O-C_2H_4-O-C_2H_4-.