JPH0823690B2 - Photopolymerizable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel photopolymerizable composition, and more particularly to a photopolymerizable composition having improved cured film strength obtained.

(Prior Art) In the production of printed wiring boards, a dry film type photoresist is capable of easily forming a photoresist layer having a uniform film thickness, and can be used as a through-hole etching resist in a so-called tenting method. Is better than A hole called a through-hole is pre-drilled, a metal layer such as copper is formed inside it, and a dry film is laminated on both sides of a double-sided board having conductor layers on both sides. Pattern exposure is performed so that a slightly larger resist film is formed. After development, etching is performed to remove unnecessary metal layers. At this time, the metal in the through hole is protected by the resist film provided on the upper portion of the through hole, so that both surfaces of the formed printed circuit board can be electrically conducted. The dry film resist used for such a purpose is required to stably adhere to the substrate under the conditions where development and etching are performed, and that the etching liquid does not enter into the through hole. Have not always been satisfactory. Generally, increasing the exposure dose at the time of pattern formation improves the tent film strength, but as the exposure dose increases, the resolution decreases and it is difficult to form a high-density pattern, and the time required for exposure increases and productivity decreases. .

A method has been proposed in which the adhesion to the substrate at the land around the through hole is increased to improve the reliability of the tenting (JP-A-59-113432, JP-A-60-12543, and JP-A-59-1669).
No. 44, JP-A-50-19135), these methods involve the inclusion of various substances that promote adhesion in the photosensitive layer, often resulting in poor development, defective resist removal in later steps, etc. May be given.

A method in which a halogen-based additive is used in order to increase the strength of the cured film after exposure of the photosensitive layer has also been proposed (Japanese Patent Laid-Open No. Sho 60)
-15972, JP-A-57-60327, JP-A-59-78339),
This method is also useful for increasing the sensitivity and color development.
However, in the case of a photoresist having a relatively high sensitivity, the deterioration of storage stability becomes a problem. Especially when the photosensitive layer is in contact with the copper surface, the dark reaction in the unexposed area tends to be remarkable.

(Problems to be Solved by the Invention) The present invention provides a photopolymerizable composition that solves the above-mentioned problems of the prior art and provides high cured film strength.

(Means for Solving Problems) The present invention provides (1) an addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, (2) a photoinitiator, and (3) a benzene represented by the following formula [I]. Derivative (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 7 carbon atoms. To an aralkyl group having 20 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, an acyl group having 1 to 12 carbon atoms or a carboxyl group, and R ₆ and R ₇ each independently represent a hydrogen atom or halogen. An atom, an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, A, B, D and E are each independently -CO-, -O-, -S-, (R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms), (R ₁₀ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group having 1 to 6 carbon atoms), and a photopolymerizable composition containing the same.

The addition weight compound contained in the photopolymerizable composition according to the present invention has a boiling point of 100 ° C. or higher at normal pressure. When the boiling point is lower than 100 ° C under normal pressure, the addition-polymerizable compound is volatilized and volatilized when the solvent contained in the system is removed by drying or irradiated with an actinic ray. This is because it is not preferable. The addition-polymerizable compound is preferably soluble in the organic solvent used in order to form a uniform composition with the photoinitiator and the like.

Organic solvents include, for example, acetone, methyl ethyl ketone,
Toluene, chloroform, methanol, ethanol, 1,
1,1-trichloroethane or the like is used.

The addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure is obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid, for example, diethylene glycol di (meth) acrylate (diacrylate or dimethacrylate). Meaning of acrylate, the same shall apply hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-propanediol Di (meth) acrylate, 1,3-butanediol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis (4 -Acry Roxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, etc. obtained by adding α, β-unsaturated carboxylic acid to a glycidyl group-containing compound,
For example, Shin-Nakamura Chemical Co., Ltd. trade name BPE-500 (mixture of 2,2-bis (4-methacryloxypolyethoxyphenyl) propane), trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A di Glycidyl ether di (meth) acrylate, trade name MECHPP manufactured by Osaka Organic Chemical Co., Ltd., γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-
Unsaturated amides such as phthalates such as methylenebisacrylamide, ethylenebisacrylamide, 1,6-hexamethylenebisacrylamide, vinyl esters such as divinylsuccinate, divinyladipate, divinylphthalate, divinylterephthalate, divinylbenzene-
Examples include 1,3-disulfonate.

This addition-polymerizable compound is used alone or in combination of two or more.

As the photoinitiator used in the present invention, conventionally known photoinitiators can be used. For example SP Purpose (SPPapp
as) Chapter 1 of "UV Curing: Science and Technology" and SP Purpose (SPPappas) Chapter "UV Curing: Science and Technology"
Various compounds described in Chapter 1 of Science and Technology vol.II) can be used. For example, benzophenone, thioxanthone, chlorothioxanthone, alkyl-substituted thioxanthones, benzyl, 4,
4'-dimethoxybenzyl, 9,10-phenanthrenequinone, 9,10-anthraquinone, azo compounds and acylphosphines. Further, a binary initiator in which benzophenones, thioxanthones, 3-ketocoumarins are combined with a reducing agent such as an amine can also be preferably used. For example, benzophenone and triethanolamino, benzophenone and Michler's ketone, benzophenone and 4,4 '.
-Bis (diethylamine) benzophenone, 2,4-diethylthioxanthone and isopentyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, 3,3'-carbonylbis (7-diethylamino) coumarin And N, N-diethylaniline, 3-benzoyl-7-methoxycoumarin and N-phenylglycine, and 4'-cyanobenzoyl-5,7-dimethoxycoumarin and N-phenylglycine. Also, as photo-reducing dyes, rose bengal, erythrosine,
Eosin, riboflavin, thionine and the like can be used alone or in combination with various reducing agents. 2 photoinitiators
More than one species may be used.

In the present invention, the benzene derivative represented by the above formula [I] is used, and examples thereof include phenylcyclohexane, 4'-bromophenylcyclohexane, (p-anisyl) cyclohexane, 4-phenyl-cyclohexanone, 2
-Phenyl cyclohexanone, 3-phenyl cyclohexanone, 4-phenyl piperidine, 2-phenyl piperidine, 3
-Phenyl piperidine, N-acetyl-4-phenyl piperidine, N-acetyl-2-phenyl piperidine, N-acetyl-3-phenyl piperidine, 4-phenyl tetrahydropyran, 2-phenyl tetrahydropyran, 3 -Phenyltetrahydropyran, 4- (p-bromophenyl) tetrahydropyran, 2- (p-bromophenyl) tetrahydropyran, 3- (p-bromophenyl) tetrahydropyran, 4- (p-anisyl) tetrahydropyran, 3- (p −
Anisyl) tetrahydropyran, 2- (p-anisyl) tetrahydropyran, 4-cyclohexylbenzoic acid, ethyl 4-cyclohexylbenzoate, butyl 4-cyclohexylbenzoate, 4-cyclohexylacetophenone, 3-cyclohexylacetophenone, 2 -Cyclohexylacetophenone, 4-phenyltetrahydrothiopyran, 2-phenyltetrahydrothiopyran, 3-phenyltetrahydrothiopyran, 6-phenyl-1,3-dioxane, 5-phenyl-1,3
-Dioxane, 6-phenyl-1,4-dioxane, 2-phenylglutaric anhydride, γ-phenyl-δ-valerolactone, α-phenyl-δ-valerolactone β-phenyl-δ-valerolactone, α-phenyl- Examples include δ-valerolactam, β-phenyl-δ-valerolactam, γ-phenyl-δ-valerolactam, 2-phenylmorpholine, 2-phenyl-1,4-oxathiane and the like.

These benzene derivatives can be used alone or in combination of two or more kinds.

In the present invention, 0.01 to 20 parts by weight of a photoinitiator and 0.01 part of a benzene derivative represented by the above formula [I] are added to 100 parts by weight of the addition-polymerizable compound having a boiling point of 100 ° C. or higher at the above normal pressure. It is preferably used in the range of 20 to 20 parts by weight.

The photopolymerizable composition of the present invention may optionally contain one or more high molecular weight organic polymers. The high molecular weight organic polymer is thermoplastic and has a molecular weight of 10,000 to 700,0
Those having 00 are preferred. For example, the following is used.

(A) Copolyester Produced from polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol and the like and polyvalent carboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid, adipic acid and the like. Made copolyester.

(B) Vinyl polymer Methacrylic acid, acrylic acid, methacrylic acid or alkyl ester of acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate, β-hydroxyethyl (meth) acrylate, styrene, vinyltoluene, vinyl chloride,
Homopolymers or copolymers of vinyl monomers such as vinyl butyral.

(C) polyformaldehyde (D) polyurethane (E) polycarbonate (F) nylon or polyamide (G) cellulose ester such as methyl cellulose,
By adding a high molecular weight organic polymer to the ethylcellulose photopolymerizable composition, properties such as adhesion to a substrate, chemical resistance and film property can be improved. This high molecular weight organic polymer is in the range of 80% by weight or less based on the total weight of the high molecular weight organic polymer and the addition polymerizable compound. 80% by weight
If the amount exceeds the above range, photocuring does not proceed sufficiently, which is not preferable.

The photopolymerizable composition according to the present invention may also contain coloring substances such as dyes and pigments, if necessary. Known coloring substances are used, for example, fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria visual blue, malachite green, night green.
B, Spiron blue, etc.

The photopolymerizable composition according to the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance stability during storage. Examples of such substances include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, pyridine, nitrobenzene, and arylphosphite.

The photopolymerizable composition according to the present invention may contain other additives known to be used in the photopolymerizable composition, for example, additives such as a plasticizer and an adhesion promoter.

The photopolymerizable composition of the present invention can be applied to a support and exposed to actinic rays to produce a printing plate, or can be used as a photoresist for forming a circuit by etching or plating. The actinic radiation source used is 250 nm to 550
Those that generate actinic radiation with a wavelength of nm are used.

Such light sources include carbon arc lamps, mercury lamps,
There are xenon arc lamps, argon glow lamps, argon ion lasers, etc. As the support, an organic polymer film such as a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a metal plate such as a copper plate, an aluminum plate and an iron plate, an insulating plate having a copper foil on its surface (glass epoxy base material, paper epoxy base material) Materials, paper phenol base materials, etc.) are used.

(Function) In the present invention, when the above component (2) polymerizes the component (1) by the action of light, the component (3) adjusts the degree of polymerization to relieve the stress due to shrinkage accompanying polymerization. It is presumed that the strength of the obtained cured film is increased.

(Effects of the Invention) The photopolymerizable composition according to the present invention is a photopolymerizable composition that gives a high cured film strength, and is useful for forming a dry film resist having excellent tenting property in the production of a printed circuit board, for example. is there.

(Example) An example of the present invention will be described. Here, parts and% indicate parts by weight and% by weight.

Examples Preparation of Photopolymerizable Composition Acrylic polymer (methacrylic acid / methylmethacrylate / butyl methacrylate / 2-ethylhexyl acrylate = 23/51/6/20 weight part copolymer, polymerization average molecular weight about 90,000) 40% ethyl cellosolve solution of 120 parts BPE-500 (Shin-Nakamura Chemical Co., Ltd., trade name, mixture of 2,2-bis (4-methacryloxypolyethoxyphenyl) propane) 25 parts MECHPP (Osaka Organic Chem. Co., Ltd., trade name, γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate) 8.5 parts Tetraethylene glycol dimethacrylate 2.5 parts Hydroquinone 0.04 parts Benzophenone 3.8 parts 4,4′-bis (diethylamino) ) Benzophenone 0.17
Parts Methyl ethyl ketone 20 parts As a comparative example, a photopolymerizable composition to which the compounds shown in Table 1 were added and a comparative example to which these compounds were not added were prepared as coating solutions.

Each coating solution was applied onto a 25 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name “Lumilar”) using a bar coater, and dried for about 3 minutes with a hot air convection dryer at 100 ° C. A polymerizable element was obtained. The thickness of the dried photopolymerizable composition layer was 40 μm.

Next, using a laminator that pressurizes and heats with a rubber roll to laminate, make sure that the photopolymerizable composition layer and the copper surface are in contact with both sides of the glass epoxy double-sided copper clad laminate having a clean surface 3.2 mm diameter through hole The temperature of the rubber roll is 160 ℃
The photopolymerizable element was laminated as.

Both surfaces of the stacked samples were irradiated with a 3 KW ultra-high pressure mercury lamp (HMW201B manufactured by Oak Co.). Then remove the polyethylene terephthalate film and remove it by 1% at 30 ℃.
Spray development treatment was performed for 60 seconds with a Na ₂ CO ₃ aqueous solution, and air drying was performed at room temperature for 1 hour in the dark. At the center of the cured film on the through hole of this sample, a rheometer (FRM, manufactured by FUDOH, NRM-2010J-
CW) was used to read the force (g / cm ² ) when the steel rod with a diameter of 2.0 mm entered and the film broke, and it was taken as the tenting strength. The results are shown in Table 1.

It is shown that high cured film strength is obtained in the examples.

Claims (2)

[Claims] 1. An addition-polymerizable compound having a boiling point of 100 ° C. or higher at atmospheric pressure, (2) a photoinitiator and (3) a benzene derivative represented by the following formula [I] (wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are respectively Independently hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkoxycarbonyl group having 1 to 12 carbon atoms,
An aryl group, an aryloxy group, an acyl group having 1 to 12 carbon atoms or a carboxyl group, and R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or 7 to 20 carbon atoms. Aralkyl group of A, B, D and E are each independently -CO-, -O-, -S-, (R ₈ and R ₉ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms), (R ₁₀ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 1 to 6 carbon atoms). 2. A high molecular weight organic polymer, wherein the high molecular weight organic polymer is 80% by weight or less based on the total weight of the high molecular weight organic polymer and the addition-polymerizable compound. The photopolymerizable composition described.