JP2002173510A - Photopolymerization compound system for photosensitive resin composition, photosensitive resin composition and photosensitive element using the same resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of producing a cured film excellent in strengths, elongation and resistance to mechanical impact and a photosensitive element. SOLUTION: This photopolymerization compound system for photosensitive resin compositions comprises (C) a photopolymerization compound containing a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid as an essential component and having at least one polymerizable ethylenically unsaturated group in the molecule and (D) a compound represented by general formula (II) [wherein R2 represents hydrogen atom or methyl group; R3 represents hydrogen atom or a 1-4C alkyl group; R4 represents a 4-14C alkyl group; h is an integer of 3-20; k is an integer of 1-3]. This photosensitive resin composition comprises the photopolymerization compound system for photosensitive resin composition. This photosensitive element is obtained by laminating the resin composition on a support film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition and a photosensitive element using the same.

[0002]

2. Description of the Related Art Conventionally, there are two methods of manufacturing a printed wiring board, a tenting method and a plating method. The tenting method protects the copper through-hole for mounting the chip with a resist, forms an electrical circuit through etching and resist peeling, whereas the plating method deposits copper in the through-hole by electroplating, Protected by solder plating,
In this method, an electric circuit is formed by removing and etching a resist. The tenting method does not include various steps such as degreasing, substrate cleaning, acid cleaning, and activation as compared with the plating method, and the resist does not directly come into contact with a strongly acidic or strongly basic aqueous solution. It is industrially useful because unnecessary troubles are avoided and the process is simplified.

Further, in recent years, as the density of wiring of a printed wiring board has been increased and the precision thereof has been increased, the tent reliability has become a problem in the tenting method due to the formation of irregularly shaped through holes and the narrowing of through hole lands. In addition, the plating method requires resistance to plating chemicals. To improve the chemical resistance, a method using a photopolymerizable compound having an isocyanurate ring is disclosed in JP-A-61-77844. JP-A-62-290705, JP-A-61-1
No. 4212, JP-A-59-222480, JP-A-1-14190, JP-A-57-55914, JP-A-5-216224, JP-A-5-27
It is described in, for example, Japanese Patent No. 3754, but it has a problem that the cured film is hard and brittle, so that it is difficult to achieve compatibility with tent reliability.

[0004]

SUMMARY OF THE INVENTION The first aspect of the present invention provides a photosensitive resin composition which produces a cured film having excellent strength, elongation and mechanical impact resistance. Claim 2
The invention described above provides the effects of the invention described in claim 1 and provides a photosensitive resin composition having excellent sensitivity. The invention according to claim 3 is a photosensitive element which is excellent in formability, sensitivity, etc. of a cured film excellent in strength, elongation, mechanical shock resistance, and also excellent in handleability, workability, environmental preservation, etc. Is provided.

[0005]

The present invention provides (A) and (a)
20 to 40% by weight of methacrylic acid and alkyl acrylate and / or alkyl methacrylate 6
An alkali-developable vinyl copolymer compound having a weight average molecular weight of 130,000 to 20,000 obtained from 0 to 80% by weight as a copolymer component and (b) methacrylic acid 20 to
A weight-average molecular weight of 30,000 to 40% by weight and 60 to 80% by weight of an alkyl acrylate and / or an alkyl methacrylate obtained as a copolymer component.
120,000 of the alkali-developable vinyl copolymer compound and (a) component / (b) component in 10/90 to 90
A film-imparting polymer mixed at a weight ratio of / 10,
(B) a photopolymerization initiator, (C) a general formula (I)

Embedded image [Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents —CH ₂ CH ₂ O—, and Y represents

Embedded image And Z represents a hydrocarbon group having 2 to 16 carbon atoms;
m, p and q are each independently an integer of 1 to 14]
A photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, comprising a compound represented by the following formula as an essential component: and (D) a general formula (II)

Embedded image [Wherein, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkyl group having 4 to 14 carbon atoms, and h represents 3 to 20 is an integer, and k is an integer of 1 to 3].

In the present invention, the mixing ratio of the component (A), the component (B), the component (C) and the component (D) is set so that the total amount of the component (A), the component (C) and the component (D) is 100 Component (A) is from 40 to 80 parts by weight, component (B) is from 0.1 to 20 parts by weight, component (C) is from 5 to 55 parts by weight, and component (C). The present invention relates to the photosensitive resin composition, which contains the compound represented by the general formula (I) in an amount of 5 parts by weight or more and the component (D) in an amount of 5 to 15 parts by weight. Also, the present invention
The present invention relates to a photosensitive element obtained by laminating the photosensitive resin composition on a support film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention contains the above components (A), (B), (C) and (D) as essential components. The film-imparting polymer used as the component (A) in the present invention is obtained by copolymerizing (a) 20 to 40% by weight of methacrylic acid and 60 to 80% by weight of an alkyl acrylate and / or an alkyl methacrylate. Alkali-developable vinyl copolymer compound having a weight average molecular weight of 130,000 to 200,000 and (b) 20 to 40% by weight of methacrylic acid and 60 to 80% by weight of alkyl acrylate or alkyl methacrylate
Is obtained as a copolymer component.
0 to 120,000 of an alkali-developable vinyl copolymer compound and (a) component / (b) component in 10/90 to
The mixture was mixed at a weight ratio of 90/10.

[0008] The alkyl acrylate or methacrylic acid ester as a copolymer component preferably has 1 to 12 carbon atoms in the alkyl moiety. Examples thereof include methyl acrylate, methyl methacrylate, and ethyl acrylate. Examples include esters, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate.

The alkali-developable vinyl copolymer compound having a weight average molecular weight of 130,000 to 200,000, which is the component (a) in the component (A), gives strength to the cured film,
Weight average molecular weight of component (b) 30,000-12
The 000 alkali-developable vinyl copolymer compound breaks down the cured product in the peeling step. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene. (A) Component /
The weight ratio of the component (b) is preferably from 10/90 to 90/10. Outside this range, sufficient strength cannot be obtained in the cured film, and the cured product is not fragmented in the peeling step, causing a problem of sticking to a machine, a substrate, or the like.

The amount of the component (A) is as follows:
The total amount of the components (C) and (D) is preferably 40 to 80 parts by weight based on 100 parts by weight, and 50 to 7 parts by weight.
It is more preferably 0 parts by weight, particularly preferably 55 to 65 parts by weight. When the amount is less than 40 parts by weight, the photocured product becomes brittle, and when used as a photosensitive film, the coating properties tend to be poor. When the amount exceeds 80 parts by weight, sufficient sensitivity tends not to be obtained. .

Examples of the photopolymerization initiator which is the component (B) used in the present invention include aromatic ketones (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone, etc.), benzoin ether (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc.) Benzoin derivatives (methylbenzoin, ethylbenzoin, etc.), benzyl derivatives (benzyldimethylketal, etc.), 2,4,5-triarylimidazole dimer (2- (o-chlorophenyl) -4,5-diphenylimidazole dimer) Body, 2- ( - chlorophenyl) -4,
5-di (m-methoxyphenyl) imidazole dimer,
2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, -(2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2
-(P-methylmercaptophenyl) -4,5-diphenylimidazole dimer, etc.), acridine derivative (9-
Phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and the like. These are used alone or in combination of two or more.

The amount of the component (B) is as follows:
Preferably, the amount is 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (C) and (D).
More preferably 5 to 10 parts by weight, 0.20 to
Particularly preferred is 7 parts by weight. When the blending amount is 0.
If the amount is less than 1 part by weight, the sensitivity tends to be insufficient.
If the amount exceeds 0 parts by weight, the light absorption on the surface of the composition at the time of exposure tends to increase and the internal light curing tends to be insufficient.

In the present invention, the component (C) includes:
The compound represented by the general formula (I) is used as an essential component. In the general formula (I), Z which is a hydrocarbon group having 2 to 16 carbon atoms includes, for example, an alkylene group (ethylene group,
Hexylene group, 2-ethylhexylene group, trimethylhexylene group, decylene group, etc., cycloalkylene group (cyclohexylene group, bicyclohexylene group, etc.), arylene group (phenylene group, biphenylene group, naphthylene group, etc.) and the like. No. Examples of commercially available compounds include, for example, UA-13 (trade name of Shin-Nakamura Chemical Co., Ltd.)
and so on.

Examples of the photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule other than the compound represented by the general formula (I) include, for example, polyhydric alcohols containing α, β-unsaturated Compounds obtained by reacting carboxylic acids (polyethylene glycol diacrylate, polyethylene glycol dimethacrylate (having 2 to 14 ethylene groups), trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate), a compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound (bisphenol A dioxyethylene diacrylate) Acrylate,
Bisphenol A dioxyethylene dimethacrylate,
Bisphenol A trioxyethylene diacrylate,
Bisphenol A trioxyethylene dimethacrylate, bisphenol A decaoxyethylene diacrylate, bisphenol A dioxyethylene diacrylate such as bisphenol A decaoxyethylene dimethacrylate, bisphenol A dioxyethylene dimethacrylate, trimethylolpropane triglycidyl ether triacrylate, Bisphenol A diglycidyl ether diacrylate, bisphenol A diglycidyl ether dimethacrylate, etc.). These compounds may be used alone or in combination of two or more.

The amount of component (C) is as follows:
The amount is preferably 5 to 55 parts by weight, more preferably 7 to 40 parts by weight, and more preferably 10 to 35 parts by weight, based on 100 parts by weight of the total of the components (C) and (D). Particularly preferred. If the amount is less than 5 parts by weight, sufficient sensitivity may not be obtained, and the strength and elongation of the cured film may not be obtained. If the amount exceeds 55 parts by weight, sufficient sensitivity may not be obtained. Further, the component (C) preferably contains the compound represented by the general formula (I) in an amount of 5 parts by weight or more, and if the compounding amount of the compound represented by the general formula (I) is less than 5 parts by weight, And sufficient cured film strength and elongation cannot be obtained.

The ethylenically unsaturated compound represented by the general formula (II) used as the component (D) in the present invention comprises 1 to
It has a structure in which three alkyl groups (R ⁴ ) are bonded to a phenoxy group. Those having more than 4 alkyl groups (k) are difficult to obtain and have poor developability.
The alkyl group has 4 to 14 carbon atoms. When the carbon number is 3 or less, the developer resistance and the adhesive strength to copper decrease, and when the carbon number is 15 or more, the developability also decreases. A halogen atom, a nitrogen atom-containing group, an aryl group, an alkylene group, and the like may be bonded to the phenoxy group. Specific examples of this compound include nonylphenoxypolyethyleneoxyacrylate, nonylphenoxypolyethyleneoxymethacrylate, butylphenoxypolyethyleneoxyacrylate, and butylphenoxypolyethyleneoxymethacrylate. In the general formula (II), R ³ is a hydrogen atom. The total (h) of the number of repeating units of the ethyleneoxy group and the number of repeating units of the propyleneoxy group in which R ³ is a methyl group is an average of 3 to 20, and preferably 4 to 16. If this number is less than 3, the flexibility of the cured film will be poor. On the other hand, when it exceeds 20, the developer resistance of the photosensitive layer is reduced.

The amount of the component (D) is as follows:
The amount is preferably 5 to 15 parts by weight, more preferably 5 to 12 parts by weight, and more preferably 5 to 10 parts by weight based on 100 parts by weight of the total amount of the components (C) and (D). Particularly preferred. If the amount is less than 5 parts by weight,
Elongation of the cured film tends to be poor, and if it exceeds 15 parts by weight, the crosslinking density tends to decrease, and the strength of the cured film tends to decrease.

The photosensitive resin composition of the present invention is applied on a metal surface, for example, a surface of copper, nickel, chromium or the like, preferably on a copper surface, as a liquid resist, dried and coated with a protective film. Or can be used as a photosensitive element. Although the thickness of the photosensitive resin composition layer varies depending on the use, it is preferably 10 to 100 μm in thickness after drying. When used as a liquid resist, an inert polyolefin film such as polyethylene or polypropylene is used as a protective film. The photosensitive element can be obtained by applying a photosensitive resin composition on a support film such as polyester and drying it, followed by lamination.

If necessary, the photosensitive resin composition may contain acetone, methyl ethyl ketone, methylene chloride, toluene,
Methanol, ethanol, propanol, butanol,
It can also be mixed with a solvent such as methylene glycol, ethylene glycol, propylene glycol, monomethyl ether, or a mixed solvent thereof, and applied as a solution.

The photosensitive resin composition layer is irradiated with actinic rays in a pattern through a negative or positive mask pattern called an artwork, and then developed with a developing solution.
This is used as a resist pattern. As a light source of the actinic ray used at this time, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp or the like that effectively emits ultraviolet rays is used. As the developing solution, one that is safe and stable and has good operability is used, and a diluted solution of sodium carbonate or the like is used for an alkali developing type photoresist. Development methods include a dip method and a spray method, and a high-pressure spray method is most suitable for improving resolution.

[0021]

Next, the present invention will be described by way of examples.

Examples 1 and 2 and Comparative Examples 1 to 7 The components (A) and (B) shown in Table 1 and other components shown in Table 2 were mixed to prepare solutions.

[0023]

[Table 1]

[Table 2]The obtained solution was added with the component (C) shown in Tables 3 and 4 and
Dissolving the component (D) to obtain a solution of the photosensitive resin composition
Was. In Tables 3 and 4, UA-13 is a general formula.
In (I), R¹= CH₃, X = C₂H₄O, Y =
C₃H₆O, Z = (CH ₂)₆, N = 1, p = 9, q =
9. Compound of m = 1 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name UA-
13), and M-113 is a compound represented by the general formula (II):
R²= R³= H, R⁴= C₉H₁₉, H = 4, k = 1
Compound (Alonix M, manufactured by Toa Gosei Chemical Industry Co., Ltd.)
-113), and NK-4G is tetraethyleneglycol.
Cole dimethacrylate (Shin Nakamura Chemical Co., Ltd., trade name N
K-4G) shown.

[0024]

[Table 3]

[Table 4] Next, the solution of the photosensitive resin composition was uniformly applied on a 25 μm-thick polyethylene terephthalate film,
The photosensitive element was obtained by drying with a hot air convection dryer at 100 ° C. for 10 minutes. The dried film thickness of the photosensitive resin composition layer was 40 μm. Subsequently, exposure was performed at 70 mJ / cm ^{2 using} a 3 kW high-pressure mercury lamp (HMW-201B, manufactured by Oak Manufacturing Co., Ltd.). After removing the polyethylene terephthalate film and the polyethylene film, a cured film (1 cm wide)
X length 2 cm), and the results are shown in Table 5.

[0025]

[Table 5] As is clear from the results shown in Table 5, in Examples 1 and 2 of the present invention, both the tensile strength and the elongation are large, but in Comparative Examples 1 to 7, the components (A), (C) and (D) The composition lacked any of the components, and it was found that both the tensile strength and the elongation were lacking.

[0026]

According to the photosensitive resin composition of the present invention, a cured film having excellent strength, elongation and mechanical impact resistance can be obtained. The photosensitive resin composition according to the second aspect has the effects of the photosensitive resin composition according to the first aspect, and is further excellent in sensitivity. The photosensitive element according to the third aspect is excellent in formability, sensitivity and the like of a cured film having excellent strength, elongation and mechanical shock resistance, and is also excellent in handling, workability, environmental preservation and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H05K 3/00 H05K 3/00 F (72) Inventor Tatsuya Ichikawa 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical (72) Inventor Yuichi Kamakura 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant F-term (reference) 2H025 AA01 AA13 AB15 AC01 AD01 BC43 BC44 CA00 FA17 4J027 AC02 AC03 AC04 AC06 AC09 AJ02 AJ08 BA19 BA20 BA23 BA26 BA28 CA03 CB10 CC05 CD10 4J100 AL08Q AL62P AL63P AL66P BA02P BA03P BA08P BA08Q BA09P BA38P BC43Q BC45P CA04 CA23 DA50 DA51 DA52 JA38

Claims (5)

[Claims] 1. A light having at least one polymerizable ethylenically unsaturated group in the molecule, which contains, as an essential component, a compound obtained by reacting (C) a polyhydric alcohol with an α, β-unsaturated carboxylic acid. A polymer compound; (D) a compound represented by the general formula (I
Compound represented by I) [Wherein, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkyl group having 4 to 14 carbon atoms, and h represents 3 to 20 is an integer, and k is an integer of 1 to 3]. 2. The light for a photosensitive resin composition according to claim 1, wherein the compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol has two ethylenically unsaturated groups in the molecule. Polymer compounds. 3. A compound represented by the general formula (I):
A compound represented by the following formula: [Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X represents —CH ₂ CH ₂ O—, and Y represents And Z represents a hydrocarbon group having 2 to 16 carbon atoms;
m, p and q are each independently an integer of 1 to 14]
The photopolymerizable compound for a photosensitive resin composition according to claim 1, which comprises: 4. A photosensitive resin composition comprising the photopolymerizable compound for a photosensitive resin composition according to claim 1. 5. A photosensitive element obtained by laminating the photosensitive resin composition according to claim 4 on a support film.