JPS60195171A - Ultraviolet-curing ink composition - Google Patents

Abstract

PURPOSE:To provide the titled ink composition containing a specific polyurethane polyacrylate, etc., a specific acrylate, a photo-crosslinkable oligomer, etc., having excellent adhesivity to the substrate and electrical insulation, and useful as a solder resist for printed circuit board. CONSTITUTION:The objective composition can be prepared by compounding (A) a polyurethane polyacrylate having plural acryloyl groups and plural urethane bonds in one molecule and obtained by the reaction of a polyisocyanate compound with a polyhydroxy compound as a chain extender and a hydroxyacrylate, and/or an epoxy polyacrylate having plural acryloyl groups in one molecule and obtained by reacting an epoxy resin with acrylic acid, with (B) hydroxypivaric acid neopentyl glycol di(meth)acrylate, (C) other photo-crosslinkable oligomer and/or monomer, and (D) a photo-polymerization initiator. The weight ratios of the components A:B:C:D are preferably (20-80):(5-90):(0-50):(3-15).

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an ultraviolet curable ink composition, particularly an ultraviolet curable screen ink composition useful as a solder resist for flint wiring boards.

[Prior art]

In recent years, from the perspective of streamlining the drying process, there has been an active movement in the printed wiring board industry to replace conventional hot air dry curing inks with ultraviolet curing inks, with the most progress being made in replacing solder resist inks. Ultraviolet curing ink has the advantage of faster curing speed than conventional hot air dry curing ink, and because it is cured only by ultraviolet light, there is no need for the plate to dry on the screen plate. The actual situation is that the required electrical properties, particularly electrical insulation properties, are inferior to conventional hot air dry curing inks.

[Purpose of the invention]

An object of the present invention is to provide an ultraviolet curable screen ink composition that is particularly useful as solder paste for printed wiring boards and has excellent adhesion to printed circuit boards and excellent electrical properties, particularly electrical insulation.

(A) 1 obtained by reacting a polyisocyanate compound, a polyhydroxy compound, and a hydroxyacrylate;
Polyurethane polyacrylate having two or more 7-acryloyl groups and two or more urethane bonds in the molecule, and/or having two or more acryloyl groups in one molecule obtained by reacting an epoxy resin with acrylic acid. The main components are epoxy polyacrylate, (B) hydroxypiparic acid ester neobentyldalicol di(meth)acrylate, (C) other photocrosslinkable oligomers and/or photocrosslinkable monomers, and ■) photopolymerization initiator. This is achieved by using an ultraviolet curable ink composition.

[Embodiment]

The above (A) used in the ultraviolet curable ink composition of the present invention.
Components ) to (D) will be explained in more detail by showing specific examples. In this specification, (meth)acrylate refers to either acrylate or methacrylate, and (meth)acrylic acid refers to either acrylic acid or methacrylic acid.

First, among component (A), polyurethane polyacrylate is obtained by reacting a polyisocyanate compound with a polyhydroxy compound and hydroxyacrylate that are chain extenders, and contains two or more acryloyl groups and two acryloyl groups in one molecule. This is a compound having the above urethane bond. Examples of polyisocyanate compounds include diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, lysine twinocyanate, inphorone diisocyanate, dimer acid diisocyanate, and trimethylhexane diisocyanate; There are many kinds, and these 7]
? Polyisocyanates, which are reaction products of lysocyanate compounds and low-molecular polyols, can also be used.

Examples of polyhydroquine compounds that can be used as chain extenders include neopentyl glycol, 2,2,4-)limethyl-1゜3-
′! Tantanediol, 1,6-hexanediol, triethylene glycol, trimethylolpropane, penquerythritol, diintaerythritol, hydrogenated bisphenol A1 Combination of bisphenol A and/or hydrogenated bisphenol A with ethylene oxide or zolopyrene oxide Examples include dioxy-7 alkyl ether, polyglolactone siol, a low molecular weight compound having a hydroxyl group at the terminal or side chain, and 39-lyester polyol.

Examples of the 1-hydroxy acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxy-3-(2-ethylhexyloxy7) f-robyl acrylate. I cut it,
Among the components (4), epoxy polyacrylate is a compound having two or more acryloyl groups in one molecule obtained by reacting an epoxy resin with acrylic acid. type,
Bisphenol F type, bisphenol S type, phenol novolac type, and hydantoin tights are added with oil.Among the specific compounds of component (A), those showing particularly good properties include polyurethane polyacrylate. So, as a button extender poly and doxy compound, use nooxyalkyl ether to bisphenol. Examples include compounds using epoxy resins.

In addition, component (c) is a component that provides the basic properties of the ink film, and has good curing properties when exposed to ultraviolet rays in the air, as well as imparts toughness to the film.

The blending amount of component (A) is the total amount of components (A) to 0) 1
00 weight and 11 parts, preferably 20 to 80 weight parts.

The component (B), hydroxyl phosphoric acid ester neotakuntyl glycol di(meth)acrylate, is hydroxyl 1? Barin! It is a condensation reaction product of an esterified product of counterfeit toneopentyl glycol and (meth)acrylic acid, and this compound has a low viscosity and is used to adjust the viscosity of a composition. It can provide superior adhesion and insulation properties compared to other monomers that have been used. The blending amount of component (B) is preferably 5 to 90 parts by weight per 100 parts by weight of the total amount of components (B) to (B).

Next, component (C') is a photocrosslinkable oligomer and/or photocrosslinkable monomer that can be blended into components (A) and (B), and it improves the hardness, flexibility, and viscosity of the resulting film. Specific compounds include tetramethylolmethanetetra(meth)acrylate, trimethylolzolopanetri(meth)azilylate, pentaerythritoltri(meth)acrylate,
1,6-hexanethiol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl glycol zo(meth)acrylate, triethylene glycol di(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, 2 -Ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-vinyl-2-pyrrolidone, carpitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, inbornyl (meth)acrylate
Examples include acrylate, dicyclomethyl (meth)acrylate, 2- and droxinoropyl (meth)acrylate, and the like. The blending amount of component (C) is preferably 0 to 50 parts by weight per 100 parts by weight of the total amount of components (A3 to A3).

Component (D), the photopolymerization initiator t, is an essential component for UV curing the UV curable ink composition of the present invention, and may be used alone or in combination.

Specifically, benzoin methyl ether, benzoin ethyl ether, pensoin isoglobil ether, pentuin-n-butyl ether, R-benzoin penzophenone,
Chloranthraquinone, 2,2-shedquin acetophenone, mixed system of benzophenone and tertiary amine, 2-
Mixed system of chlorothioxanthone and tertiary amine, 2,
Examples include 2-dimethoxy-2-phenylacetophenone, 1-hydroxychlorohexylphenyl ketone, 2-ethylanthraginone, 1-chloroanthraquinone, 2-chloroanthraquinone, and the like. Among these, anthraquinone compounds are preferred because they not only have high activity against ultraviolet rays but also can provide a commercially viable ink film. The blending amount of component (2) is preferably 3 to 15 parts by weight based on 100 parts by weight of the total amount of components (4) to (D).

The ultraviolet curable ink composition of the present invention containing these (--(D)) as a main component may contain other saturated polymers for the purpose of further improving adhesion, flexibility, corrosion resistance, etc. For example, (meth)acrylic acid ester copolymer, vinyl chloride-vinyl acetate copolymer, polyester, etc.Furthermore, in order to improve printability as a screen ink and for coloring, ordinary fillers, Antifoaming agents, leveling agents, anti-stringiness agents, dyes, pigments, etc. may also be mixed.

Examples of the light source used for curing the ultraviolet curable ink composition of the present invention include low H; mercury lamps, cylinder pressure mercury lamps, xenon lamps, arc lamps, liupa lamps, etc.;
A 450 mμ lamp is effective.

Historically, the ink composition has been exposed to ultraviolet rays for good hardening in deep areas. (It is also possible to improve the deep curing property by heating after one shot.

Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, parts mean parts by weight.

[Actual 1! 1 Example 1] Addition of phenolic epoxy resin and acrylic acid as polyacrylate Q, h 5
OR5' and trimethylolzolopane triacrylate 2
To 5 parts, 25 parts of hydroxypiparic acid ester neoantyl glycol diacrylate was added to adjust the viscosity.
The resin component contains 5 parts of 2-ethyl anthraquinone, 50 parts of talc, and 1 part of phthalocyanine green as a photopolymerization initiator.
In addition, three rolls were mixed and mixed to obtain ultraviolet hardening type ink 16.1. 15 ink on copper clad plate
Coat to a thickness of μ, 1 (1, pressure mercury stroke (80w/ltn)
) Three lights were used to fire 1i for 10 seconds from a distance of about 20 crn. This coated plate was used to evaluate the properties shown in the table below.

[Example 2] Instead of epoxy 7 diacrylate in Example 1, tolylene diisocyanate was used as the polyurethane compound, a globylene oxide adduct of bisphenol A was used as the diliol compound, and 2-hydroxyethyl acrylate was used as the hydroxyl group-containing acrylate. An ultraviolet curing type ink 2 was obtained in the same manner as in Example 1, except that polyurethane polyacrylate made by Vta was used. Applying the ink in the same manner as in Example 1 and curing it,
Morosu characteristics were evaluated. The results are also shown in the table.

[Example 3] 25 parts of epoxy polyacrylate used in Example 1 and 2 parts of polyurethane polyacrylate used in Example 2
5 parts: trimethylolzoro-guntriacrylate 25
25 parts of methacryloxybiparyl methacryloxypiparate was added as a diluent in the same manner as in Example 1, and then in the same manner as in Examples 1 and 2, UV-curable ink A3 was added. was coated in the same manner as in Actual M+ Examples 1 and 2, cured, and evaluated. The results are shown on the envelope.

[Comparative example j]

The diluent hydroxybi-9-phosphate nemopentyl glycol diacrylate used in Example 1 was modified to use 2-hydroxyethyl methacrylate. I got UV curing ink & 4. Can you use this ink at the same level as Example 1? Sξi+iL, cured and evaluated.

The claims are also shown in Section 6.

[Comparative Example 2] Instead of the epoxy polyacrylate used in 1, acrylic acid was condensed with a polyester consisting of phthalate and neopentyl dalicol.
Polyester that can be used, IC! Using real acrylate”? J, the outside is the same as the actual Mi pHi 11) and the ultraviolet curing ink 116.5 is I4. Using this ink, do the same as in Example 1? Ma≧I01 Curing and evaluation of the cured product were performed.

The results were also shown to the public.

Table @1 Gopan Cellotape Peeling Test @2 Solder Bath Dig Test @3 Applied Voltage 500V 1 Minute Value Measurement From this table, it can be seen that the ultraviolet curable ink composition of the present invention has excellent adhesion, heat resistance, and It can be seen that it has a high electrical insulation resistance value.

[Effects of the Invention] As demonstrated in the above-mentioned "Examples", the ultraviolet curable ink composition of the present invention is suitable as a resist resist for printed wiring boards, and has excellent heat resistance as well as heat resistance.
It has excellent practical properties I'+13, such as excellent adhesion to the glint wiring board and extremely good electrical insulation.

Claims (5)

[Claims] (1) (A) A polyurethane having two or more acryloyl groups and two or more urethane bonds in one molecule obtained by reacting a polyisocyanate compound, a polyhydroxy compound, and a hydroxyacrylate, I? Epoxy polyacrylate having two or more acryloyl groups in one molecule obtained by reacting polyacrylate and/or epoxy resin with acrylic acid, (B) Hydroxypiparic acid ester neobentyl glycol (meth) An ultraviolet curable ink composition comprising as main components an acrylate, (C) a photocrosslinkable oligomer and/or a photocrosslinkable monomer of flμ, and (D) a photopolymerization initiator. (2) Among (A) components, 7j? The ultraviolet curable ink composition according to claim 1, wherein the urethane polyacrylate is obtained using bisphenol A dioxyalkyl ether as the polyhydroxy compound. (3) Among the components (A), the epoxy polyacrylate is obtained by using an epoxy resin having a phenol novilac structure as the epoxy resin, Claims (1) or (2) The ultraviolet curable ink composition described in 1. (4) The ultraviolet curable type according to any one of claims (1) to (3), wherein the photocrosslinkable monomer of component (C) is trimethylolpropane tri(meth)acrylate. Ink composition. (5) Claims (1) to (4) in which the photopolymerization initiator of component (D) is an anthraquinone compound.
The ultraviolet curable ink composition according to item 1.