JPS61173242A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To form a photopolymerizable compsn. increased in photosensitivity by adding a combination of benzophenone, a specified aminophenyl ketone, and a specified amino compd. as a photopolymn. initiator to a compsn. contg. a compd. having an ethylenically unsatd. group. CONSTITUTION:The photopolymerizable compsn. contains 10-90wt% compd. (component 1) having >=100 deg.C b.p. at normal pressure, and at least one kind of ethylenically unsatd. group, 2-15wt% benzophenone (component 2), 0.01-5.0wt% compd. represented by formula I, 0.01-1.0wt% compd. (component 4) represented by formula II, and 0-80wt% thermoplastic org. polymer (component 5). Benzophenone (2) in combination with components (3), (4) is essential component, and they can obtain extremely increased photosensitivity, while the storage stability of the photopolymerizable compsn. is retained. As the compd. of component (3), e.g., p,p'-dimethylaminobenzophenone, etc., are used, and as the compd. of component (4), e.g., N-phenylglycine, etc., are used.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photopolymerizable composition, and more particularly 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 to actinic light can be shortened. Conventionally, various methods have been used.

For example, a method of adding a photoinitiator or sensitizer to a photopolymerizable composition containing an ethylenically unsaturated group-containing compound has been used to increase photosensitivity. These photoinitiators or sensitizers include polynuclear quinones such as 2-ethylanthraquinone and 2-t-butylanthraquinone;
Aromatic ketones such as hensifhenone and 4,4'-bis(dimethylamino)benzophenone, and benzoin derivatives such as benzoin methyl ether and benzoin ethyl ether are used. However, the photosensitivity of conventional photopolymerizable compositions obtained using these photoinitiators or sensitizers was not necessarily sufficient.

Furthermore, in order to increase photosensitivity, a combination of an aromatic ketone such as aminophenyl ketone and a 2,4.5-triarylimidazole dimer may be used (Japanese Patent Publication No. 4-38403, US Pat. No. 731,733). ), using a combination of aminophenyl ketone and an active methylene compound or an amino compound (Japanese Patent Publication No. 49-11
No. 936, US Pat. No. 877,853) are known.

However, none of these conventional methods provides 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 Problems) As a result of intensive research, the present inventors have discovered that a combination of benzophenone, a specific aminophenyl ketone, and a specific amino compound is used as a photoinitiator, and the ethylenically unsaturated group-containing The present invention was achieved by discovering that the above object can be achieved by adding the compound to a composition containing the compound.

The present invention provides a compound 1 having a boiling point of 100°C or higher at normal pressure and having at least one ethylenically unsaturated group.
0-90% by weight, (2) benzophenone 2-15% by weight
, (3) General formula (1) (wherein R1, R2, R3 and R
4 means a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) 0.01 to 5.0% by weight (4)
Compounds represented by the general formula % formula % () (in the formula, R5 is a phenyl group which may be substituted with an alkyl group, and R4 means a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) 0゜01-1 0% by weight and (5) 0 to 80% by weight of a thermoplastic organic polymer.

1 at normal pressure used in the photopolymerizable composition of the present invention.
Examples of the compound (component (1)) having a boiling point of 00°C or higher and containing at least one ethylenically unsaturated group include compounds obtained by adding α,β-unsaturated carboxylic acids to polyhydric alcohols. compounds, such as tetraethylene glycol di(meth)acrylate (meaning methacrylate or acrylate, the same applies hereinafter), polyethylene glycol di(meth)acrylate (meaning methacrylate or acrylate, the same applies hereinafter),
~14), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, polypropylene glycol di(meth)acrylate ( (having 2 to 14 propylene groups), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, compound obtained by adding α,β-unsaturated carboxylic acid to a glycidyl group-containing compound , for example, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc., polyhydric carboxylic acids, such as phthalic anhydride, and substances having hydroxyl groups and ethylenically unsaturated groups, such as β-hydroxyethyl (meth) Esterified products with acrylate etc., alkyl esters of acrylic acid or methacrylic acid, such as (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester etc.

The blending amount of these components (1) is 10 to 90% by weight, preferably 20 to 80% by weight. This amount is 10% by weight
If the amount is less than 90% by weight, the photocured product will be brittle and sufficient physical properties will not be obtained, and if it is more than 90% by weight, the amount of other components will be relatively small and sufficient photosensitivity will not be obtained.

Component (2) benzophenone is an essential component used in combination with component (3) and component (4), and when these three components are used in combination, it can be used while maintaining the storage stability of the photopolymerizable composition. , a greatly increased photosensitivity is obtained.

The blending amount of component (2) is 2 to 15% by weight, preferably 3% by weight.
~10% by weight. When this amount is less than 2% by weight, there is no significant effect on increasing photosensitivity, and when it is more than 15% by weight, the storage stability of the photopolymerizable composition is reduced.

Examples of the compound represented by the general formula (I) as component (3) include p,p'-dimethylaminobenzophenone and p,p'-diethylaminobenzophenone. The blending amount of component (3) is 0.01 to 5.0% by weight,
Preferably it is 0.1 to 3.0% by weight. This amount is 0.
If it is less than 0.01% by weight, sufficient photosensitivity will not be obtained, and if it is more than 5.0% by weight, light absorption on the surface of the composition will increase during exposure, resulting in insufficient internal photocuring. Become.

Examples of the compound represented by the general formula (If) as component (4) include N-phenylglycine, N-phenylglycine ethyl ester, N-phenylglycine methyl ester, N-phenylglycine butyl ester, and N-methylphenylglycine. Ethyl ester etc. are used.

The blending amount of component (4) is 0.01 to 1.0% by weight, preferably 0.1 to 0.7% by weight. When this amount is less than 0.01% by weight, a sufficient increase in photosensitivity cannot be obtained, and when it is more than 1.0% by weight, the storage stability of the photopolymerizable composition is reduced, and furthermore, the composition There is a strong odor due to the gas that evaporates when heat is applied.

Examples of thermoplastic organic polymers include (meth)acrylic@(meaning methacrylic acid or acrylic acid, the same hereinafter) copolymers of alkyl esters and (meth)acrylic acid, and (meth)acrylic acid alkyl esters. (meta)
Copolymers of acrylic acid and vinyl monomers that can be copolymerized with these are used. Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid ethyl ester, and (meth)acrylic acid ethyl ester.
Examples include butyl acrylate, 2-ethylhexyl (meth)acrylate, and the like. In addition, (meth)acrylic acid alkyl esters and vinyl monomers that can be copolymerized with (meth)acrylic acid include (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylethyl ester, and (meth)acrylic acid diethyl ester. , methacrylic acid glycidyl ester, 2°2.
1-) Lifluoroethyl (meth)acrylate, 2,2
, 3.3-tetrafluoropropyl (meth)acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like. Furthermore, as the thermoplastic organic polymer, homopolymers of the above compounds can also be used, and copolyesters such as terephthalic acid,
Polyesters of isophthalic acid and sebacic acid, etc., copolymers of butadiene and acrylonitrile, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, etc. can also be used.゛The blending amount of the thermoplastic organic polymer, which is component (5), is 0 to 0.
80% by weight, preferably 20-70% by weight. The use of a thermoplastic organic polymer improves coating properties and the film strength of the resulting cured product.

If this amount is more than 80% by weight, the other components will be relatively small, resulting in a decrease in photosensitivity. Further, the weight average molecular weight of this thermoplastic organic polymer is preferably 10,000 or more from the viewpoint of the coating properties and film strength. The above ingredient (1),
Component (2), component (3), component (4) and component (5)
is used in an amount within the above weight % range such that the total amount is 100 weight %.

The photopolymerizable composition of the present invention can contain a thermal polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, and t-butylcatechol.

The photopolymerizable composition of the present invention may also contain colorants such as dyes and pigments. Examples of coloring agents include Tsukushin, Auramine Base, Crystal Hioresotho, and Big 1.
- Reapia Blue, Malachite Green, Methyl Orange, Asocide Violet) RRH, etc. are used.

Furthermore, known additives such as plasticizers, adhesion promoters, and talc may be added to the photopolymerizable composition of the present invention, and halogen compounds such as carbon tetrabromide may be added so as to discolor exposed areas. Combinations with leuco dyes may also be added.

The photopolymerizable composition of the present invention can be dissolved and mixed using a solvent that dissolves each of the above-mentioned components, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, methyl alcohol, and ethyl alcohol. By this, a uniform solution is obtained.

The photopolymerizable composition of the present invention can be used by applying it as it is to a substrate such as a copper plate, drying it, exposing it to actinic light, and photocuring it. Alternatively, the composition in solution form may be applied onto a polyethylene terephthalate film, dried, and then laminated onto a substrate and photocured for use.

As a light source of active light used in photocuring, one that emits light with a wavelength of 300 to 4.50 nm is used, and for example, mercury vapor arc, carbon arc, and xenon arc are preferable.

(Effects of the Invention) The photopolymerizable composition of the present invention exhibits high photosensitivity and also has excellent solution storage stability.

The photopolymerizable composition of the present invention can be used as a photoresist for etching or plating, using a photocured film as a relief, or using a copper-clad laminate as a substrate.

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

Examples 1 and 2 Tetraethylene glycol diacrylate 400g1
Malachite green 2g1 barium sulfate 100g,
Solution A was obtained by blending 10 g of methyl alcohol and 30 g of dimethylbormamide. Add the first
A solution of the photopolymerizable composition of the present invention was obtained by melting the photoinitiator at the blending ratio shown in the table.

This solution was then 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 under 20 marks of a 7Kw high-pressure mercury lamp at a conveyor speed of 3 m/min, and the number of passes until there was no tack to the touch on the surface was measured. The results are shown in Table 1. It shows that the smaller the number of passes, the higher the photosensitivity. For comparison, the number of passes until curing was also investigated in the case where N-phenylglycine was not used as a photoinitiator, and the results are also shown in Table 1.

From the results in Table 1, it can be seen that the photopolymerizable composition of the present invention was found in Comparative Example 1.
It is shown that the photosensitivity is higher than in the case of .

Examples 3 and 4 Methyl methacrylate-1-/methacrylic acid/2-ethylhexyl acrylate (weight ratio 60/20/20) copolymer (weight average molecular weight - 80,000) 52 g, tetraethylene glycol diacrylate 10 g, Poly (P#5) Dimethacrylate of oxyethylated bisphenol A (
Shin-Nakamura Chemical Industry Co., Ltd. BPE-10) 30g, malachite green 0.2g, hydroquinone 0.1g
, 1.0 g of leuco crystal violet, 0.5 g of carbon tetrabromide, 10 g of toluene, 130 g of methyl cellosolve, 5 g of methyl alcohol, and 10 g of chloroform to obtain 8 g of solution B24B (non-volatile content total 93.8 g). A photoinitiator was dissolved in this solution B in the proportions shown in Table 2 to obtain a solution of the photopolymerizable composition of the present invention.

Next, this solution was uniformly applied to a 25 μm thick polyethylene telescope film and dried for about 5 minutes in a hot air convection dryer at 100° C. to obtain a photopolymerizable element. The film thickness of the photopolymerizable composition after drying was 25 μm.

On the other hand, a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material with copper foil (thickness 35 μm) laminated on both sides, was used.
The copper surface of MCL-E-61) was polished with #800 sandpaper, washed with water, and dried with an air stream. The resulting copper-clad laminate was heated to 60°C, and the photopolymerization was applied on the copper surface. The elements were laminated while being heated to 120°C. The degree of odor generated at that time was evaluated. The adhesion between the photopolymerizable composition layer and the copper surface was good in all cases.

Next, using a negative film on the substrate thus obtained, exposure was performed at 50 m and J/d using a 3 Kw high pressure mercury lamp (manufactured by Oak Seisakusho Co., Ltd., Fenisox-3000). At this time, in order to be able to evaluate the photosensitivity, a negative film was made so that the amount of light transmission decreased step by step (the first step is an optical density of 0.05, and the optical density increases by 0.15 with each step). Step tablet) was used.

The polyethylene terephthalate film was then removed, and the unexposed areas were removed by spraying a 2% aqueous sodium carbonate solution at 30° C. for 50 seconds. Furthermore, the photosensitivity of the photopolymerizable composition was evaluated by measuring the number of steps of the photocured film formed on the copper-clad laminate. The higher the number of steps in this step, the higher the photosensitivity.

On the other hand, storage stability was evaluated by putting the solution of the photopolymerizable composition in a sealed container, storing it in a dark place at 40° C., and checking the number of days until gelatinization occurred.

These results are shown in Table 2 together with Comparative Examples 2 to 11.

Margin below (note) 1) ○: Does not gel even if stored at 48 hr/40°C or higher.

x: Gel within 48hr/40℃ Ru.

2) ○: No odor occurs to the extent that it affects work.

×: Odor generated to the extent that work becomes difficult.

The results in Table 2 show that the photopolymerizable composition of the present invention has high photosensitivity and also has excellent solution storage stability. In the case of the comparative examples, either sufficient photosensitivity cannot be obtained, or the storage stability procedure amendment (voluntary) ``December 19, 1985, Mr. Commissioner of the Japan Patent Office, et al. 1, Incident Indication'' Patent Application No. 14112 2, Name of the invention Photopolymerizable composition 3, Relationship with the case of the person making the amendment Name of patent applicant (445) Hitachi Chemical Co., Ltd. 5, Detailed description of the invention in the specification subject to the amendment Column 6, contents of amendment 1) In the third line of page 11 of the specification, "Victoria Beer Blue" is corrected to "Victoria Pure Blue."

2) In the 6th line from the bottom of page 15, the text "Glass epoxy horse chestnut" has been corrected to "Glass epoxy material."

that's all 7 each

Claims (1)

[Claims] 1. (1) Compound 1 having a boiling point of 100°C or higher at normal pressure and having at least one ethylenically unsaturated group
0-90% by weight, (2) benzophenone 2-15% by weight
, (3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1, R_2, R_3 and R_4 mean a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) (4) General formula (I
I) R_5-NHCH_2COO-R_6(II) (R_
5 is a phenyl group optionally substituted with an alkyl group, R
_6 means a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) 0.01 to 1.0% by weight of a compound and (5) 0 to 80% by weight of a thermoplastic organic polymer. Polymerizable composition.