CA1151789A - Photopolymerization type resin composition and solder resist containing the same - Google Patents

Photopolymerization type resin composition and solder resist containing the same

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Publication number
CA1151789A
CA1151789A CA000347923A CA347923A CA1151789A CA 1151789 A CA1151789 A CA 1151789A CA 000347923 A CA000347923 A CA 000347923A CA 347923 A CA347923 A CA 347923A CA 1151789 A CA1151789 A CA 1151789A
Authority
CA
Canada
Prior art keywords
type epoxy
acrylates
solder
resin composition
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000347923A
Other languages
French (fr)
Inventor
Junji Ikeda
Keiji Saeki
Tamotsu Wakahata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Application granted granted Critical
Publication of CA1151789A publication Critical patent/CA1151789A/en
Expired legal-status Critical Current

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  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE:
A photopolymerization type resin composition consisting of one or more resins selected from a group consisting of resol type epoxy-acrylates, novolak type epoxy-acrylates, resol type epoxy-methacrylates and novolak type epoxy-meth-acrylates; an unsaturated compound whose end groups of ethylene are less than those of said one or more resins; and a photo-sensitizer. The resin composition is useful for the solder-resist applied to a flexible base plates of printed circuit boards.

Description

51~7~9 BACKGROUD OF T~IE INVL~ITION:
The present invention relates to a composition which mainly consists of photopolymerization type unsaturated compounds and can be used for forming protective or solder resist films over base plates in the processes for fabrication of printed circuit boards or metal parts which must be within very close dimensional tolerances.
In the processes for fabrication of printed circuit boards, various solder-resist inks have been used in order to provide the permanent protection of circuit patterns and to avoid the formation of undesirable bridges between the component parts in the step of soldering. These inks consist mainly of epoxy, melamine, urea, alkyd resins or these resins which are modified or denatured. When they are heated, they are cured or hardened to form the protective films or coatings.
'rhe time required to cure these solder-resist inks is in general of the order of ten to twenty minutes so that they present serious pro~lem3 in the improvement of the productivity. In addition,vapour generated from organic solvents in solder-resist inks when printing and formalin vapour produced in the curing reaction spread unpleasant order, and causing the atmospheric pollution. Furthermore the contents of involatile compounds in the solder-resist inks are of the order of 60 to 80~ so that the relatively thick ink patterns must be printed or otherwise formed in order to attain the desired electrical properties and satisfactory resistance to heat and chemical compounds. As a result, it is extremely difficult to produce the solder-.:
- 2 -,, .. . . , ., , . . , .. . ., . . . , , ... _ . . _, .. . .. . .. . ....

~1517~39 resist ink patterns with desired degree of dimensional accuracies. Moreover, heating or baking of the printed solder-resist-ink patterns results in the degradation of the printed circuit boards and needs a cooling step before the heated or baked circuit boards are transferred to the next processing ~tep.
In order to overcome the above-described problems, there has been devised and used a solder-resist ink which mainly consists of monomers which have unsaturated double bonds of ethylene and form the radical bridge structure, prepolymers and a photo-sensitizer for initiating the photo-polymerization. This solder-resist ink is rapidly cured or hardened when irradiated with ultraviolet ray and may ensure the safe processing because it contains no solvent. This ink is used in printing the patterns on the rigid base plates.
The solder-resist ink described above provides excellent heat resistance to heat in the soldering step, but the cured pattern has low flexibility so that this ink cannot be applied to the flexible base plates. There is available a conventional solder-resist ink which has high flexibility, but its heat resistance is not satisfactory to be applied to the flexible base plates. The flexible ba~e plates are very thin 50 that their heat capacity is extremely low. Therefore the solder-resist inks which may be successEully applied to the flexible base plates must provide excellent heat resi~tance, and a hic~h dec~ree of adhesion to the copper foils and resin films of polyimid, polyester or epoxy resin. And the solder-resist patterns must obviously exhibit high flexibility. The flexible printed ~51789 circuit boards are advantageous in that they are light in weight and very thin in thickness and have excellent flexibility. Therefore there are advantages (1) in that more flexible layouts of circuit patterns become feasible because the limited space in the electric or electronic equipment can be effectively utilized, (2) in that the flexibility may promise the designs of novel component parts and ~3) in that the fabrication processes can be considerably simplified so that the fabrication cost can be reduced.
However, so far no solder-resist ink which may be successfully applied to the flexible circuit boards has been proposed.

S~MMA~Y OF THE INVENTION:
The primary object of the present invention is therefore to provide a photopolymerization type solder-resist ink which ensures excellent resistance to heat and high flexibility so that it is especially adapted for use with the flexible ba~e plates or circuit boards.
Briefly stated, to the above and other ends, the present invention provides a photopolymerization type resin composition consisting of one or more resin~ selected from a group of re~ol type epoxy-acrylates, novolak type epoxy-acrylates, resol type epoxy-methacrylates, novolak type epoxy-acrylates and an un~aturated compound whose end groups of ethylene are less than those of the above-described resins and a photo-sensitizer.
Re~ol or novolak type epoxy-acrylates and meth-acrylates resins used in the present invention are provided by the chemical reaction of resol type phenols or cresols having more than two epoxy groups or glycidyl ethers obtained ~ , ~

1~51~789 from phenol novolaks or cresol novolaks and acrylic acid or methacrylic acid. Examples of glycidyl ethers are "Epikote 152 and 154", tne product of Shell Chemical Co., Ltd.;
"DER 431", the product of Dow Chemical Co; and "CIBA EPi~ 1138 and 1139", the products of JAPAN CIBA Geigy K~.
As the above unsaturated compound, the low molecular polyester resins containing acryloyl or methacryloyl groups as shown below are examplified;
(meth-) acrylic acid, 2-hydrocyl-~meth-) acrylate, 2-hydroxypropyl-(meth-) acrylate, 2-hydroxyl-(meth-) acrylate, dimethyl-aminoethyl-lmeth-) acrylate, neopentyglycol-di-(met4-) acrylate, triethyleneglycol-di-~meth-) acrylate, trimethylolpropane-tri-(meth-) acrylate, pentaerythritol-tetra~m~h-) acrylate and tetraethylene-glycol-di-~meth-) acrylate. In this specification, (meth-) acrylates refer to both acrylates and meth-acrylates.
The above low molecular polyester resins may ~e used singly or in combination according to requirement. The low molecular polyester resin containing methacryloyl groups and less end groups of ethylene than those of the above polyester resin containing acryloyl groups is a preferable material.
The photosensitizers are for example benzoin, benzoin methylether, benzoinisopropylether, benzoinbutylether, benzil, and benzophenon. These compounds are used in the preparation of the conventional photopolymerization type composition.
In addition to tne above-described constituents which are essential in photopolymerization composition of the present invention, body and coloring pigments whicll are used in the preparation of photopolymerization type paint or ink, material to endow the composition thixotropic filler, ' ~3 .. . ...

~51789 stabilizers and other suitable agents are addea and uniformly dispersed so that the film forming ability may be improved and desirable printability may be ensured. In addition, various resins such as bisphenol A type epoxy-acrylates, bisphenol F type epoxy-acrylates, urethane-acrylates and silicon acrylates may be added. In other words, the present invention is not limited to the above-described essential compounds.
In order to cure or harden the solder-resist ink of the present invention by the irradiation of light, there may be used the light sources such as conventional ultra-high-pressure mercury vapor lamps, high-pressure mercury " vapor lamps, low-pressure mercury vapor lamps, metal halide ,,; lamps, xenon lamps and chemical lamps.
,S15 DESCRIPTION OF EXAMPLES:
. ~
EXAMPLE 1:
A photopolymerization type resin composition for j'~ solder-resist ink in accordance with the present invention 20 was prepared by uniformly mixing the following constituents.
,; 1. phenol-novolak type epoxy-acrylate 12% by weight 2. ~-hydroxyethylmethacrylate35% by weignt
3. 2-functional polyester-acrylate12% by weight
4. 2-ethylanthrachinon1% by weight a~
5. ~odaflow (Monsant Co.)1% by weight
6. talc 35% by weight
7. Aerodil (SiO2 fine powder)2% by weight
8. phthalocyanine green2% by weight The obtained resin composition is completely unvolatile.

p ~1789 By silk screening using a screen of 250 to 300 mesh, the pattern was printed on a flexible base plate made of polyimid resin and cured to form a protective coating or film by irradiating for 15 seconds with a high-pressure mercury vapor lamp of 80 W/cm2. The distance between the lamp and the base plate was 10 cm.
, Thus printed and cured pattern exhibited the following properties.
1. heat resistance (in the soldering step):
260 + 5C, for lO seconds ~under the test ; procedures specified by JIS C-6481) The result was satisfactory.
, 2. flexibility (JIS P-8115):
subjected to the 180 bending with R - 0.38.
No fracture.
3. adhesion ~JIS D-0202):
Peeling test with the tape having the check-, board pattern: 100/100 4. pencil hardness ~JIS D-0202): 3~
The resin composition also has an excellent shelf life. Its propexties were found stable even after stored for more than 6 months at room temperature.
EXAMPLE 2:
~he following constituents were uniformly mixed to prepare a photopolymerization type resin composition which is 100~ involatile.
1. cresol-novolak type epoxy-acrylate 20~ by weight 2. 2-hydroxypropyl-acrylate 25~ by weight 3. 2-functional polyester-acrylate 20~ by weight - ~151789 4. benzoinisopropyl ether 1% by weight ~. Modaflow~(Monsant Co.) 1% by weight 6. calcium carbonat 30% by weight 7. Aerodil 1% by weight 8. phthalocyanine green 2~ by weight Following the procedures of EXAMPLE 1, the same result as in Example was obtained.
As described above, the solder-resist ink in accordance with the present invention has excellent heat resistance when soldering, high flexibility and a high , degree of adhesion. In addition, it has satisfactory printability in silk screening. Therefore it may be satisfactorily used with various flexible base plates.
So far the present invention has been described in S con~unctlon with the solder-resist ink used in the fabrication ,~ processes of printed circuit boards. Since, as described previously, the photopolymerization type resin composition $n accordance with the present invention have well-balanced properties such as excellent resistance to heat and chemicals, high flexibility and sensitivity, they may be used for the preparation of photopolymerization type adhesives, molding agents, paint, printing ink and so on. The present invention is therefore not limited to EXAMPLES 1 and 2 described above.

; - 8 -'E~

Claims (6)

WHAT IS CLAIMED IS:
1. A photopolymerization type resin composition consisting of one or more resins selected from a group consisting of resol type epoxy-acrylates, novolak type epoxy-acrylates, resol type epoxy-methacrylates and novolak type epoxy-methacrylates; an unsaturated compound whose end groups of ethylene are less than those of said one or more resins;
and a photosensitizer.
2. A photopolymerization type resin composition as set forth in Claim 1 wherein said unsaturated compound is a low-molecular polyester resin having acryloyl or methacryloyl groups.
3. A photopolymerization type resin composition as set forth in Claim 1 wherein said unsaturated compound is a low molecular polyester resin having methacryloyl groups and the end groups of ethylene which are less than those of a low molecular polyester resin having acryloyl groups.
4. A solder-resist-ink comprising of one or more resins selected from a group consisting of resol type epoxy-acrylates, novolak type epoxy-acrylates, resol type epoxy-methacrylates and novolak type epoxy-methacrylates; an unsaturated compound whose end groups of ethylene are less than those of said one or more resisns; a photosensitizer;
and body and coloring pigments.
5. A solder-resist-ink as set forth in Claim 4 wherein said unsaturated compound is a low molecular polyester resin having acryloyl and/or methacryloyl groups.
6. A solder-resist-ink as set forth in Claim 4 wherein said unsaturated compound consists of a low molecular polyester resin having acryloyl groups and a low molecular polyester resin having methacryloyl groups and end groups of ethylene which are less than those of said resins.
CA000347923A 1979-03-20 1980-03-19 Photopolymerization type resin composition and solder resist containing the same Expired CA1151789A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3275479A JPS55127097A (en) 1979-03-20 1979-03-20 Photocurable resin composition and solder resist
JP32754/1979 1979-03-20

Publications (1)

Publication Number Publication Date
CA1151789A true CA1151789A (en) 1983-08-09

Family

ID=12367623

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000347923A Expired CA1151789A (en) 1979-03-20 1980-03-19 Photopolymerization type resin composition and solder resist containing the same

Country Status (2)

Country Link
JP (1) JPS55127097A (en)
CA (1) CA1151789A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4771085A (en) * 1986-10-07 1988-09-13 E. I. Du Pont De Nemours And Company Curable dielectric compositions
US6399277B1 (en) 1996-06-28 2002-06-04 Vantico Inc. Photopolymerizable thermosetting resin composition

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5825371A (en) * 1981-08-06 1983-02-15 Toyobo Co Ltd Ultraviolet-curing ink composition for printed circuit
JPS59213779A (en) * 1983-04-22 1984-12-03 Meidensha Electric Mfg Co Ltd Ultraviolet-curing solder resist ink
JPS603624A (en) * 1983-06-22 1985-01-10 Takao Ono Photosensitive composition
JPS6049071A (en) * 1983-08-30 1985-03-18 Toshiba Chem Corp Marking ink
JPS61252546A (en) * 1985-05-01 1986-11-10 Ueno Kagaku Kogyo Kk Photosensitive resist ink and manufacture of ps plate by using it and method for etching this ps plate
JPH0689284B2 (en) * 1985-06-29 1994-11-09 株式会社アサヒ化学研究所 Curable resin composition for solder-resist ink
US4650743A (en) * 1985-07-31 1987-03-17 E. I. Du Pont De Nemours And Company Optical coating composition
JPS62157029A (en) * 1985-12-28 1987-07-13 Unitika Ltd Photosensitive resin composition
JP2571800B2 (en) * 1987-11-27 1997-01-16 イビデン株式会社 Photosensitive adhesive for electroless plating and printed wiring board
JP2700245B2 (en) * 1988-02-20 1998-01-19 ソマール株式会社 Curable adhesive composition
JPH0748109B2 (en) * 1988-04-01 1995-05-24 イビデン株式会社 Photosensitive resin composition
US5196296A (en) * 1989-10-06 1993-03-23 Nippon Steel Corporation Epoxy acrylate resins and photosensitive resin compositions therefrom
JP2772227B2 (en) * 1993-11-15 1998-07-02 イビデン株式会社 Printed wiring board
JP4523679B2 (en) * 1998-06-22 2010-08-11 太陽インキ製造株式会社 Green resist ink composition for printed wiring board using halogen-free color pigment
JP5245099B2 (en) * 2008-04-25 2013-07-24 独立行政法人 国立印刷局 Authenticity discriminating resin composition, authenticity discriminating ink composition and its authenticity discrimination printed matter
JP6359605B2 (en) * 2016-11-15 2018-07-18 株式会社京写 Printed wiring board

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5146159B2 (en) * 1972-02-25 1976-12-07
JPS5421546B2 (en) * 1973-06-07 1979-07-31
JPS5516393B2 (en) * 1973-11-28 1980-05-01
US4003877A (en) * 1974-05-24 1977-01-18 Dynachem Corporation Photopolymerizable screen printing inks for permanent coatings prepared from aryloxyalkyl compositions
JPS5128677A (en) * 1974-09-04 1976-03-11 Alps Electric Co Ltd Suitsuchi no tanshiban no seizohoho
JPS5183760A (en) * 1975-01-20 1976-07-22 Mitsubishi Electric Corp TORANJISUTAZO FUKUKI
JPS51131706A (en) * 1975-05-08 1976-11-16 Taiyou Inki Seizou Kk Solder resist ink

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4771085A (en) * 1986-10-07 1988-09-13 E. I. Du Pont De Nemours And Company Curable dielectric compositions
US6399277B1 (en) 1996-06-28 2002-06-04 Vantico Inc. Photopolymerizable thermosetting resin composition

Also Published As

Publication number Publication date
JPS6148800B2 (en) 1986-10-25
JPS55127097A (en) 1980-10-01

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