JPS61126138A - Photo-curable resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which is lowly odorus and gives photo- cured articles having excellent flexibility, adhesion and resistance to heat, water and solvents, containing a specfic SH group-contg. high-molecular compd., a polyene and a photosensitizer. CONSTITUTION:A photo-curable resin compsn. contains a SH group-contg. high- molecular compd. of formula I, a polyene and a photosensitizer. In the formula, R1 is a redidue of a polymer precursor contg. n active hydrocarbon atoms and having formula II; R2 is a residue of a polyisocyanate compd. of formula III; R3 is a residue of a polymercaptan compd. of formula IV; A is a residue of a compd. contg. active hydrogen and olefinically unsaturated group and having formula V; k is 1-3; l is 1-3; m is 1-3; n is 1-4; p is 0-1; n+p=2-4; P, Q, R are each H, lower alkyl; X, Y, Z are each H, halogen, alkyl, aryl, etc.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a resin composition that is cured by light.

(Prior art) Polythiol-polyene resin compositions, which are conventional photocurable photosensitive materials, have been used as ultraviolet curable paints because they cause little oxygen damage during curing and the film obtained by curing is strong. , photosensitive resin plates, adhesives, etc.

However, the use of monomeric polythiols such as pentaerythritol tetrakis (β-mercaptopropionate) described in JP-A-49-95702 has the drawbacks of strong odor and poor film flexibility and pliability. are doing. In addition, reaction products of di(β-mercaptopropionic acid) polypropylene ether glycol described in JP-B No. 46-29525 and urethane prepolymer and trimethylolpropane tris (β-mercaptopropionate) described in JP-A-57-158230 are also available. The use of polythiol polymers, such as those described above, reduces bad odor and provides good flexibility and pliability, but has the drawbacks of poor adhesion to substrates, heat resistance, weather resistance, water resistance, and solvent resistance. have.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks of conventional products, and improves flexibility and
The object of the present invention is to provide a low-odor photocurable resin composition that provides a photocured product with good flexibility, adhesion, heat resistance, weather resistance, water resistance, and solvent resistance. “(Means and effects for solving the problem) In order to achieve the above object, the present inventors have conducted intensive research and found that a resin consisting of a specific 8H group-containing polymer compound, a polyene, and a photosensitizer. The present inventors have discovered that the composition is a photocurable resin composition that can overcome the drawbacks of conventionally known polythiol-polyene resin compositions, and have completed the present invention.

That is, the present invention provides residues of the general formula (wherein R1 is a prepolymer cyanate compound R1+NC0)rn+ having R active hydrogens
8 is a +4 group in the remainder of the polymercaptan compound R, (SH), and A is active hydrogen, olefinic unsaturation, and k
is an integer from 1 to 3, l is an integer from 1 to 3, and door is an integer from 1 to 3.
is an integer of 1 to 4, P is O or an integer of 1 to 3, and the sum of 1 and P is 2 to 4.

Also, P.

Q and R are each independently hydrogen or a lower alkyl group; X, Y and Z are each independently hydrogen, a halogen atom or an alkyl group, an aryl group, an aralkyl group,
It is an alkoxy group, a phenoxy group, or a halogen substituent thereof. ), a polyene, and a photosensitizer.

The SH group-containing polymer compound represented by the general formula used in the present invention can be synthesized, for example, as follows, but is not limited to the synthesis procedure described below.

General formula (wherein, R1 is the backbone of the polymer precursor, L is an integer of 1 to 4, P is an integer of 0 or 1 to 3, and the sum of L and P is 2 to 4. A polymer precursor having R active hydrogens represented by R is each independently hydrogen or a lower alkyl group is used as a starting material.

Examples of the polymer precursor include polyester polyols, polyether polyols, and polyacrylates containing hydroxyl groups.
may contain unsaturated groups such as vinyl groups or allyl groups. First, the active hydrogen in the polymer precursor and the general formula R
2+NCO), +1 (in the formula, m is an integer of 1 to 3) through an addition reaction with a polyincyanate compound, to obtain an intermediate prisoner represented by. Examples of the polyinocyanate compound include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,6
-Hexamethylene diisocyanate Triincyanate, an adduct of oyohytrimethylolpropane and tolylene diinocyanate, etc. can be used. Next, the intermediate (4) has an active hydrogen and an olefinically unsaturated group represented by the general formula,
An intermediate (B) having an olefinically unsaturated group at the terminal represented by the general formula is obtained. Examples of the compound having active hydrogen and an olefinically unsaturated group represented by the above general formula include allyl alcohol, methylallylamine, methylallyl alcohol, diallylamine, hydroxyethyl (meth)
Acrysamethylene dithiol, β, β'-dimercaptodi: Ethyl ether, trimethylolprono(ntris (β-mercaptoglopionate), pentaerythritol tetrakis (β-mercaptoglobionate), etc. with the general formula Rs(-8H) ( RIHR1H
R3HAlshima 1+ ”, rL? Pv P+ Q+R,
X, Y and 2 are as described above. ) can be obtained.

The polyene used in the present invention is a conventional polythiol-
Polyene resin compositions containing two or more olefinically unsaturated groups in the molecule can be used, such as diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butadiene di( Polyfunctional (meth)acrylates such as meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; polyallyl such as diallyl phthalate, diallyl maleate, triallyl isocyanurate, and trimethylolpropane triallyl ether Compound; N, N'-4
, 4'-diphenylmethane bismaleimide and other bismaleimide compounds; epoxy acrylate; polyurethane acrylate; polyester acrylate; liquid polybutadiene and polymer compounds containing two or more olefinically unsaturated groups among the intermediates (B), etc. They are appropriately selected from among them and can be used alone or in combination.

Photosensitizers include benzoin propyl ether, benzoin isobutyl ether, benzophenone, Michler's ketone, and chlorothioxane.

Thon, isopropylthioxanthone, benzyl dimethyl ketal, hydroxycyclohexylphenyl ketone, etc. can be used.

In order to obtain the photocurable resin composition of the present invention, the SHH-containing polymer compound, a polyene, and a photosensitizer may be mixed.

Further, fillers, plasticizers, antioxidants, adhesion promoters, solvents, titanium-imparting agents, and the like can also be used in combination with the photocurable resin composition of the present invention.

When the photocurable resin composition of the present invention is irradiated with light (ultraviolet light), free radicals generated due to decomposition of the photosensitizer, etc.
The H group-based polymer compound and the polyene are crosslinked to quickly produce a cured product, but the photocurable resin composition of the present invention
Since the above-mentioned specific SHH-containing polymer compound is used as a component, the cured product has excellent flexibility, adhesion, heat resistance, weather resistance, water resistance, and solvent resistance.

(Effects of the Invention) The photocurable resin composition of the present invention is rapidly cured by light irradiation, has flexibility, good adhesion of flexibility, and has excellent heat resistance, weather resistance, water resistance, and solvent resistance. It can be used for solder resists for printed wiring boards, cover sealing materials for flexible wiring boards, etc.

The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Incidentally, all parts in the examples are parts by weight, and all parts are % by weight.

Example 1 Polyoxypropylene triol 1 with hydroxyl value 33.3
12 parts of 2.4-tolylene diisocyanate were added to 00 parts of the mixture, and the mixture was left at 60°C for 24 hours to obtain an intermediate product. Next, 4 parts of allyl alcohol was added, and the mixture was further left at 70°C for 40 hours to obtain an olefinically unsaturated group-containing intermediate (). Then, with gradual mixing at 60°C, part β, β'-dimercapto diethyl ether', 0.5 part stt-butylperoxybenzony and 0.05 part tetramethylguanidine were added.
' part was added and left at 70°C for 20 hours to obtain SHH-containing polymer compound (1).

Example 2, SHH-containing polymer compound (1) obtained in Example 1
A photocurable resin composition (1) of the present invention was obtained by blending 10 parts of polyethylene glycol diacrylate (average molecular weight 400) as a polyene and 0.02 parts of benzophenone as a photosensitizer into 100 parts of the resulting mixture. To the obtained photocurable resin composition (1) were added 150 parts of diisodecyl 7 tallate, 200 parts of silica (average particle size 2μ) and ultrafine particulate silica (
A photocurable one-component sealant (hereinafter referred to as sealant (1)) was prepared by adding and kneading 5 parts of the mixture (average particle size ismμ), and the mixture was filled into a light-shielding container. The obtained sealing material (1) had low odor. In addition, an aluminum H-type test piece was prepared according to JI8A5758 using the obtained sealing material (1), and the test piece was cured by outdoor exposure for one month, and the adhesion, heat resistance, and heat resistance were determined by the following performance test method. Weather resistance and water resistance were evaluated. The results are shown in Table 1.

Performance test method 1) Adhesion After conducting a tensile test according to JI8A5758 to measure the initial physical properties (strength at break, elongation at break), the state of breakage after the tensile test was observed to determine the adhesion to the aluminum adherend. evaluate.

2) After holding the heat resistance test piece at 90°C for 2 weeks, perform a tensile test according to JIS A 575g to measure breaking strength and elongation at break, and observe changes from the initial physical property values before holding at 90°C.

3) After exposing the weather resistance test piece for 1200 hours using a weather meter (manufactured by Suga Test Instruments ■, WEL-8UN-HC), a tensile test was conducted according to JIS A 5758 to measure the breaking strength and elongation at break. Look at the changes from the initial physical property values before exposure.

4) After immersing the water resistance test piece in warm water at 50°C for 2 weeks, JIS A
A tensile test was conducted in accordance with 5758 to measure the breaking strength and breaking elongation, and changes from the initial physical property values before immersion were observed.

Comparative Example 1 Polyoxypropylene triol 1 with hydroxyl value 33.3
To 00 parts, 12 parts of 2.4-) lylene diincyanate was added and left at 60°C for 24 hours to synthesize an NCO group-terminated urethane prepolymer.

100 parts of the obtained NGO group-terminated urethane prepolymer was gradually added to 25 parts of trimethylolpropane-tris-β-mercaptogropionate at 100°C, and after the dropwise addition was completed, the reaction was carried out at 100°C for 6 hours to obtain a SH group-containing compound for comparison. A polymer compound (11 was obtained.

Comparative Example 2 In place of the SH group-containing polymer compound (1) in Example 2, the comparative SH group-containing polymer compound (1) obtained in Comparative Example 1 was used.
1) was used in the same amount and the amount of polyethylene glycol diacrylate was changed to 20 parts. (1)) was prepared and its performance was evaluated in the same manner as in Example 2. The results are shown in Table 2. Comparative sealing material (1) is Example 2
Compared to the sealing material (1) using the photocurable resin composition (1) of the present invention obtained in (1), elongation and flexibility are lower, and adhesiveness, heat resistance, weather resistance, and water resistance are inferior. It was something.

Example 3 Polyoxypropylene triol 9 with hydroxyl value 54.6
0 parts and hydroxyl value 53.2 polyester polyol 10
18 parts of 2,4-tolylene diisocyanate were added to the mixture, and the mixture was left to stand at 60°C for 24 hours to obtain an intermediate. Next, 7 parts of allyl alcohol was added, and the mixture was left to stand at 70°C for 40 hours to obtain an olefinically unsaturated group-containing intermediate (B). Next, β was heated to 60°C with gradual mixing.
, 10 parts of β'-dimercapto diethyl ether, 0.5 part of t-butylperoxybenzoate, and 0.05 part of tetramethylguanidine were added, and the mixture was left at 70°C for 2 hours to obtain an SH group-containing polymer compound (2). I got it.

Example 4 8H group-containing polymer compound (2) obtained in Example 3 1
00 parts, 8 parts of tetraene obtained by reacting trimethylolpropane diallyl dinitrate 2,4-tolylene diincyanate as a polyene in a ratio of 2 moles of the former to 1 mole of the latter, and 0 parts of benzophenone as a photosensitizer. ．．
2 parts were blended to obtain a photocurable resin composition (2) of the present invention.

The obtained photocurable resin composition (2) had low odor. Further, the obtained photocurable resin composition (2) was coated on a copper-clad polyimide film to a thickness of about 20 μm, and the output 2
A test piece was cured by irradiation with a KW high-pressure mercury lamp from a distance of 15 cIIL for 1 minute, and its adhesion, flexibility, heat resistance, and solvent resistance were evaluated by the following performance test method. The results are shown in Table 2.

Performance test method ①) Cut 100 1m x 15m base marks on the coating film of the adhesion test piece, perform a peel test with cellophane tape, and evaluate by the number of base marks that are peeled off. The display is (100-(number of peeled off))/100.

2) Using a flexible MIT type bending strength tester, the test piece is evaluated by the number of times it is bent until a crack appears on the surface of the test piece under a load of 1.0 to 1500 I.

3) Heat resistance Immerse in a 260°C solder bath for 20 seconds and observe peeling.

4) Solvent resistance Soaked in boiling trichlene for 15 minutes, Observe for peeling.

Comparative Example 3 Using 100 parts of pentaerythritol-nato2kis (β-mercaptoglobionate) as a polythiol, 120 parts of the same tetraene as used in Example 4 as a polyene, and 3 parts of benzophenol as a photosensitizer, A comparative photocurable resin composition was prepared, test pieces were prepared in the same manner as in Example 4, and performance was evaluated in the same manner as in Example 4.

The results are shown in Table 2, and compared to the photocurable resin composition (2) obtained in Example 4, the adhesion was better.

It had poor flexibility, heat resistance, and solvent resistance. Furthermore, the comparative photocurable resin composition had a strong unpleasant mercaptan odor.

Chapter 1 Table

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is the residue of a polymer precursor having n active hydrogens ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ And R_
2 is a polyisocyanate compound R_2-(NCO)_m_+_
1, and R_3 is the residue of polymercaptan compound R_
It is a residue of 3-(SH)_k_+_1, and A is a residue of a compound ▲Numerical formula, chemical formula, table, etc.▼ having active hydrogen and an olefinically unsaturated group. Further, k is an integer from 1 to 3, l is an integer from 1 to 3, m is an integer from 1 to 3, n is an integer from 1 to 4, and p
is 0 or an integer from 1 to 3, and the sum of n and p is 2 to 4. Further, P, Q and R are each independently hydrogen or a lower alkyl group, and X, Y and Z are each independently hydrogen, a halogen atom or an alkyl group,
It is an aryl group, an aralkyl group, an alkoxy group, a phenoxy group, or a halogen substituent thereof. 1. A photocurable resin composition comprising an SH group-containing polymer compound represented by the following formula, a polyene, and a photosensitizer.