TWI495686B - A stabilized polyene-polythiol-based hardening resin composition - Google Patents

Description

Stabilized polyene-polythiol-based curable resin composition

The present invention relates to a polyene-polythiol photocuring which can be used in the fields of printing plates or color comparison color proofs, color filters, solder resists, photo-curing inks and the like and which can improve storage stability. Resin composition.

The photocurable resin composition is used in various aspects such as a printing plate, a color matching sample ticket, a color filter, a solder resist, and a photocurable ink. In particular, in recent years, from the viewpoints of such applications, environmental problems, energy saving, work safety, production costs, etc., the most characteristic of the photocurable resin composition is room temperature hardenability, quick-drying property, solvent-free, etc. The sex composition is undergoing many research and development. In the development of color filters, pigment-dispersed photoresists for color filters have been studied for the purpose of improving productivity or high precision. In addition, the color comparison sample ticket or the printing plate was developed for the purpose of speeding up the plate making and high definition. Moreover, solder resists for printed substrates have also been studied.

In these applications, the requirements for the photohardenable resin composition are increasing, and those who seek to harden with lower energy, those who harden more quickly, can form finer patterns, have deeper depth of hardening, and preserve Those with higher performance have been asked. The photocurable resin composition is mainly composed of a photopolymerization initiator composition, a compound having an ethylenically unsaturated bond which is cured by a polymerization reaction, and various additives, and various types can be used depending on the application.

The photocurable composition is a mercaptan such as pentaerythritol tetrakis(3-hydrothiopropionate) (trade name: QX40, manufactured by Mitsubishi Chemical Corporation) for reasons of high sensitivity and high adhesion. Compound.

However, the photocurable resin composition using a thiol compound is highly sensitive, and conversely, since the reactivity is too high, there is a problem of sacrificing preservation stability.

Japanese Patent Publication No. 2010-024255 (Patent Document 1) discloses a urethane (meth)acrylate compound having three or more ethylenically unsaturated groups in a molecule, a thiol compound, and two The active energy ray-curable resin composition of cerium oxide showed excellent hardness or hardenability of the coating film, but the preservation stability was not investigated.

JP-A-2009-051936 (Patent Document 2) discloses a curable property of a compound (A) obtained by reacting a diene compound with a hydrogen sulfhydryl group-containing organodecane compound and a thiol compound (B). In the composition, it is described that a cured product having excellent curability and excellent storage stability can be provided, but it is insufficient in obtaining long-term storage stability.

JP-A-2008-184514 (Patent Document 3) discloses an ultraviolet curable resin composition containing a condensate obtained by hydrolyzing and condensing an alkoxysilane, and a compound having a secondary thiol group. However, the assessment of preservation stability was carried out at room temperature, 30 days and mild conditions. In order to obtain high temperature and long-term preservation stability is not sufficient.

A thiol-ene composition having a stabilization system is disclosed in JP-A-8-504879 (Patent Document 4, WO09500579), and one of the options for the stabilization system has been described using 4-methoxyphenol. A free radical scavenger such as hydroquinone or a monoalkyl ester of hydroquinone, benzoquinone or naphthoquinone. Further, a suitable free radical scavenger is described as 4-methoxyphenol, but in practical use, the effect of stabilization of 4-methoxyphenol and naphthoquinone is low, and long-term preservation stability cannot be obtained at high temperatures. .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2010-024255

[Patent Document 2] JP-A-2009-051936

[Patent Document 3] JP-A-2008-184514

[Patent Document 4] Japanese Patent Publication No. 8-504879

An object of the present invention is to provide a photocurable resin composition which is excellent in high sensitivity and storage stability and which can be used in a wide blending ratio of a polyolefin or a polythiol.

As a result of intensive research, the present inventors have found that a photocurable resin composition containing a thiol compound, a compound containing an ethylenically unsaturated double bond, and a compound having a specific naphthalene skeleton as a stabilizer is directly maintained. The high-sensitivity characteristic of the polyene-polythiol-based photocurable resin composition during photocuring can suppress the olefin-thiol reaction during storage and prevent gelation, and can obtain good storage stability and finish. this invention.

In other words, the present invention relates to the polyene-polythiol-based photocurable resin composition according to any one of [1] to [10] below.

[1] A curable resin composition comprising: a thiol compound, a compound having an ethylenically unsaturated double bond having two or more unsaturated double bond groups, and a formula (1)

【化1】

(wherein R ⁵ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms; and at least 2 of R ⁵ to R ⁸ are a hydroxyl group or Alkoxy group having 1 to 3 carbon atoms)

The compound shown.

[2] The curable resin composition according to the above [1], wherein R ⁵ to R ⁸ in the compound represented by the above formula (1) each independently represent a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group. At least two of R ⁵ to R ⁸ are a hydroxyl group or a methoxy group.

[3] The curable resin composition according to the above [1] or [2], wherein the compound represented by the above formula (1) is 4-methoxy-1-naphthol, 1,4-two Methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-2-methyl-1-naphthol, 4-methoxy-3-methyl-1-naphthol, 1,4-two Methoxy-2-methylnaphthalene, 1,2-dihydroxynaphthalene, 1,2-dihydroxy-4-methoxynaphthalene, 1,3-dihydroxy-4-methoxynaphthalene, 1,4- One or two or more compounds selected from the group consisting of dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, and 1,4-dihydroxy-2-methylnaphthalene.

[4] The curable resin composition according to any one of the above [1], wherein the compound represented by the above formula (1) is 4-methoxy-1-naphthol.

[5] The curable resin composition according to any one of the above [1] to [4] wherein the content of the compound represented by the above formula (1) is relative to the thiol compound and the ethylenically unsaturated double The total mass of the bond compound is from 1 to 20000 wtppm.

[6] The curable resin composition according to any one of [1] to [5] wherein the thiol compound has two or more of the formula (2)

[Chemical 2]

(wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms, m is an integer of 0 to 2, and n is 0 or 1) a thiol compound based on the above, wherein the compound containing an ethylenically unsaturated double bond has two or more formula (3)

[化3]

(In the formula, R ³ and R ⁴ each independently represent a compound containing an ethylenically unsaturated double bond represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms).

[7] The curable resin composition according to the above [6], wherein one of R ¹ and R ² in the group represented by the formula (2) represents an alkyl group having 1 to 10 carbon atoms, and the other The person represents a hydrogen atom.

[8] The curable resin composition according to any one of [1] to [7] wherein the aforementioned thiol compound is represented by the formula (4)

【化4】

(wherein R ¹ , R ² , m and n are in the same meaning as above)

An ester compound of a thiol group-containing carboxylic acid and a polyfunctional alcohol is shown.

[9] The curable resin composition according to the above [8], wherein the polyfunctional alcohol is an alkylene glycol having a branched carbon number of 2 to 10, diethylene glycol, dipropylene glycol, glycerin, or the like. Hydroxymethylpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, norbornyl dimethanol, 2,2-bis[4-(2-hydroxyethyloxy)phenyl]propane, hydrogenation A compound selected from the group consisting of bisphenol A, 4,4'-(9-fluorenylene)bis(2-phenoxyethanol) and gin(2-hydroxyethyl)trimeric isocyanate.

[10] The curable resin composition according to the above [6], wherein the compound having an ethylenically unsaturated double bond having two or more groups represented by the above formula (3) is an acrylic group or a methacrylic acid. One or more compounds having a reactive double bond selected from the group consisting of a vinyl group and an allyl compound.

The polyene-polythiol-based photocurable resin composition of the present invention has excellent storage stability, and even if it is added by a stabilizer, it does not inhibit the reactivity of the composition, and can be a polyene or a polythiol. The wide blending ratio is used, so it can be used in many applications such as printing plates or color proofs, color filters, solder resists, photo-curing inks, and the like.

[Formation for implementing the invention]

Hereinafter, the form for carrying out the invention will be specifically described.

The thiol compound used in the present invention is a compound having a -SH group, and preferably has two or more compounds of -SH group, and more preferably has 2 to 4 groups of -SH groups.

The thiol compound used in the present invention is not particularly limited, but preferably has the formula (2)

【化5】

Two or more thiol compounds are shown.

In the above formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² may be linear or branched, and may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. Isobutyl, tert-butyl, n-hexyl, n-octyl and the like are preferably a methyl group or an ethyl group.

Examples of the aromatic group having 6 to 10 carbon atoms represented by R ¹ and R ² include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a 1,3,5-trimethylphenyl group, and a naphthyl group.

m represents an integer from 0 to 2, preferably 0 or 1.

n represents 0 or 1, and is preferably 0.

Further, it is preferable that m+n is 1.

The thiol compound used in the present invention is preferably a secondary or tertiary thiol compound in which at least one of R ¹ and R ² is an alkyl group having 1 to 10 carbon atoms. Further, from the viewpoint of adjusting the light sensitivity or the storage stability to a desired range, it is more preferable that one of R ¹ and R ² is a hydrogen atom, and the other is a 2-stage thiol compound having an alkyl group having 1 to 10 carbon atoms. .

The thiol compound used in the present invention is preferably of the formula (4)

【化6】

An ester compound of a thiol group-containing carboxylic acid and a polyfunctional alcohol is shown.

In the above formula (4), R ¹ , R ² , m and n have the same meanings as described above.

The polyfunctional alcohol is a compound having two or more hydroxyl groups.

Specific examples of the polyfunctional alcohol include branched alkylene glycol having 2 to 10 carbon atoms such as 1,4-butanediol, diethylene glycol, and dipropylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, norbornyl dimethanol, 2,2-bis[4-(2-hydroxyethyloxy)phenyl]propane, hydrogenated diol A, 4, 4 '-(9-Amidino) bis(2-phenoxyethanol) and ginseng (2-hydroxyethyl) trimeric isocyanate.

The preferred polyfunctional alcohol is a 2 to 4 functional alcohol, more preferably 1,4-butanediol, tris(2-hydroxyethyl)trimeric isocyanate, pentaerythritol or trimethylolpropane.

Specific examples of the thiol compound used in the present invention include, for example, ethylene glycol bis(3-hydrothiopropionate), 1,2-propanediol (3-hydrothiopropionate), and trimethylol. Propane tris(3-hydrothiopropionate), ethylene glycol bis(3-hydrothiobutyrate), 1,2-propanediol (3-hydrothiobutyrate), trimethylolpropane III (3-Hydroxythiobutyrate), ethylene glycol bis(2-hydrothiobutyrate), 1,2-propanediol bis(2-hydrothioisobutyrate) or trimethylolpropane (2-Hexylthioisobutyrate), pentaerythritol tetrakis(3-hydrothiobutyrate), 1,3,5-tris(3-hydrothiobutyloxyethyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, 1,4-bis(3-hydrothiobutyloxy)butane, bisphenol A bis(3-hydrothiopropionic acid Ester), bisphenol A bis(3-hydrothiobutyrate), trisphenol methane (3-hydrothiopropionate), trisphenol methane (3-hydrothiobutyrate), but The invention is not limited to this. It is easy to harden with a small amount of exposure, and pentaerythritol tetrakis(3-hydrothiobutyrate) and 1,3,5-tri (3) can be suitably used for the reason that the effect of the stability obtained by the present invention is large. -Hexylthiobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,4-bis(3-hydrothiobutyloxy) ) Butane.

The thiol compound used in the present invention can also be easily obtained from a commercially available product. The thiol compound which is commercially available is pentaerythritol tetrakis(3-hydrothiopropionate) (trade name: QX40, manufactured by Mitsubishi Chemical Corporation), trade name: QE-340M, Toray Fine Chemical (share) , ether-based first-grade mercaptan (trade name: Capcure 3-800 Cognis), 1,4-bis(3-hydrothiobutyloxy) butane (trade name: Karenz MT BD1, Showa Denko) , pentaerythritol tetrakis(3-hydroxythiobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko), 1,3,5-tris(3-hydrothiobutyloxyethyl) -1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko).

A compound having an ethylenically unsaturated bond used in the present invention has a formula (3)

【化7】

Two or more compounds containing an ethylenically unsaturated bond are shown.

In the above formula (3), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms represented by R ³ and R ⁴ may be linear or branched, and may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. Isobutyl, tert-butyl, n-hexyl, n-octyl and the like are preferably a methyl group.

Examples of the aromatic group having 6 to 10 carbon atoms represented by R ³ and R ⁴ include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a 1,3,5-trimethylphenyl group, and a naphthyl group.

The compound having an ethylenically unsaturated bond used in the present invention is generally referred to as a monomer or oligomer, and a compound which can be hardened by a radical polymerization (or crosslinking) reaction. Specific examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(methyl). Acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di( Methyl) acrylate, trimethylolethane di(meth) acrylate, tetramethylolethane tri(meth) acrylate, trimethylolpropane di(meth) acrylate, trishydroxyl Propane tri(meth)acrylate, trimethylolpropane ethylene oxide addition tris(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, glycerol epoxy Propane addition tris(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol Tris(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol (meth) acrylate, sorbitol tri(meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate , pentaerythritol triallyl ether, triallyl isocyanurate, (meth) acrylate of bisphenol A alkylene oxide adduct, (meth) acrylate of trisphenol methane alkylene oxide adduct, etc. However, the present invention is not limited to this and the like. From the exposure sensitivity and the respective resistance after curing, a polyfunctional (meth)acrylate monomer is preferred. These compounds having an ethylenically unsaturated bond may be used singly or in combination of two or more. Moreover, "(meth) acrylate" also means any of "methacrylate" and "acrylate".

In the present invention, a stabilizer is added for the purpose of preventing polymerization during storage. When the stabilizer is not added, the storage stability of the highly reactive polyene-polythiol-based curable resin composition cannot be obtained.

In the present invention, the stabilizer is used in the formula (1)

【化8】

The compound shown.

In the above formula (1), R ⁵ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms.

The alkyl group having 1 to 10 carbon atoms represented by R ⁵ to R ⁸ may be linear or branched, and may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. Isobutyl, tert-butyl, n-hexyl, n-octyl and the like are preferably a methyl group.

The alkoxy group having 1 to 3 carbon atoms represented by R ⁵ to R ⁸ may, for example, be a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group, and is preferably a methoxy group.

At least two of R ⁵ to R ⁸ are a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and more preferably at least two of R ⁵ to R ⁸ are a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms.

It is preferred that the compound represented by the formula (1) is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms in the 1,4, 2, 3 or 1,2 position to obtain a radical resonance structure. The above compound is aromatic, and the stability of the compound monomer is also high. From the point of view of the compound, the substitution position is preferably 1,4.

Specific examples include 4-methoxy-1-naphthol, 1,4-dimethoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-2-methyl-1-naphthol. , 4-methoxy-3-methyl-1-naphthol, 1,4-dimethoxy-2-methylnaphthalene, 1,2-dihydroxynaphthalene, 1,2-dihydroxy-4-methyl Oxynaphthalene, 1,3-dihydroxy-4-methoxynaphthalene, 1,4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, 1,4- Dihydroxy-2-methylnaphthalene, but is not limited thereto. Among them, 4-methoxy-1-naphthol and 1,4-dihydroxynaphthalene are preferred from the viewpoints of storage stability and reactivity of the composition.

The blending ratio of the thiol compound to the compound containing an ethylenically unsaturated double bond is not particularly limited, but the thiol of the thiol compound is relative to the total amount of the C=C double bond group of the compound containing an ethylenically unsaturated double bond. The molar ratio of the base is preferably 0.0001 to 1, more preferably 0.001 to 0.5, and most preferably 0.01 to 0.1.

The amount of the stabilizer is preferably from 1 to 20,000 wtppm, more preferably from 10 to 10,000 wtppm, most preferably from 50 to 5,000 wtppm, based on the total mass of the thiol compound and the compound containing an ethylenically unsaturated double bond. Compared with the primary thiol compound, when the reactivity is low, the secondary or tertiary thiol compound is preferably from 1 to 2000 wtppm, more preferably from 10 to 1000 wtppm, most preferably from 50 to 500 wtppm. Further, the primary thiol compound is preferably from 10 to 20,000 wtppm, more preferably from 100 to 10,000 wtppm, most preferably from 500 to 5,000 wtppm. When the amount of the stabilizer is less than 1 wtppm, the stabilization effect is insufficient, and gelation occurs during storage. If the amount of the stabilizer is more than 20,000 wtppm, the hardenability tends to deteriorate during photohardening.

[Examples]

Hereinafter, the curable resin composition of the present invention will be described by way of examples and comparative examples, but the present invention is not limited to the following examples.

[Save stability test] Example 1:

Pentaerythritol tetrakis(3-hydroxythiobutyrate) (PE1, manufactured by Showa Denko Co., Ltd., SH equivalent 139 g/eq) 5.9 g, and trimethylolpropane triacrylate (light acrylate, TMPA, Kyoeisha Chemical Co., Ltd.) (stock) system, C=C double bond equivalent: 99 g/eq) 4.1 g, mixed with the total amount of C=C double bond groups of the compound containing an ethylenically unsaturated double bond, and mixed into a thiol group of the thiol compound The ear ratio is 1. Further, to the stabilizer, 0.02 g (2000 wtppm) of 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The composition was heated to 60 ° C, and after measurement to the number of days of gelation, it did not gel for 120 days.

The gelation determination method is a bottle which is stored obliquely, and if the deposit is visible, it is judged to be gelatinized.

Example 2:

The same stability test as in Example 1 was carried out except that 0.003 g (300 wtppm) of 4-methoxy-1-naphthol was used, and it was not gelled for 90 days or more.

Example 3:

The same stability test as in Example 1 was carried out except that 1,4-dihydroxynaphthalene 0.02 g (2000 wtppm) was used instead of 4-methoxy-1-naphthol, and the gelation was not carried out for 30 days or more.

Comparative Examples 1~8:

In place of 4-methoxy-1-naphthol, 2,2'-methylenebis(6-t-butyl-p-cresol) shown in Table 1 as a stabilizer was added (Comparative Example 1), 2,6-di-t-butyl-4-hydroxytoluene (Comparative Example 2), 4-methoxyphenol (Comparative Example 3), methylhydroquinone (Comparative Example 4), phenolazine (Comparative Example 5), N-nitrophenylhydroxylamine ammonium salt (Comparative Example 6), and 2,2,6,6-tetramethylhexahydropyridinyl-1-oxo (Comparative Example 7) 0.02 g (2000 wtppm), or not The same stability test as in Example 1 was carried out except for the stabilizer (Comparative Example 8). The results are shown in Table 1. In the table, "○" means "ungelatinized", "X" means "gelation", and "-" means "not determined".

[Measurement of Acrylic Reaction Rate] Example 4:

5.9 g of pentaerythritol tetrakis(3-hydrothiobutyrate) (PE1) and 4.1 g of trimethylolpropane triacrylate (TMPA) relative to a C=C double bond group of a compound containing an ethylenically unsaturated double bond The total amount, the molar ratio of the total amount of thiol groups mixed into the thiol compound is 1. For the stabilizer, 0.003 g (300 wtppm) of 4-methoxy-1-naphthol was added. Further, 0.1 g of IRG184 (manufactured by Ciha Specialty Chemicals Co., Ltd.) was added as a radical initiator. After coating with a film thickness of 30 μm on a NaCl plate, the film was formed by irradiating an exposure amount of 360 mJ/cm ² . The acrylic acid reaction rate of the film was measured. The measurement method was carried out by using FT-IR, and the reaction rate of acrylic acid was measured based on the area change ratio of the peak of the acrylic group of 810 cm ^-1 . As a result, the acrylic acid reaction rate was 94%.

Comparative Example 9:

The reaction rate of acrylic acid was measured in the same manner except that 4-methoxy-1-naphthol of Example 4 was not added. As a result, the acrylic acid reaction rate was 92%, which was the same as in Example 4.

[Relationship between blending ratio of PE1 and TMPA and preservation stability] Examples 5 to 11:

As shown in Table 2, PE1 and TMPA were mixed while changing the blending ratio, and 4-methoxy-1-naphthol was further added as a stabilizer to carry out a stability test at 40 °C. The stability test and the gelation were determined in the same manner as in Example 1. The results are shown in Table 2. In the table, "○" means "ungelatinized", "X" means "gelation", and "-" means "not determined".

Examples 12 to 14 and Comparative Examples 10 to 12:

As shown in Table 3, PE1 and TMPA were mixed while changing the blending ratio, and 4-methoxy-1-naphthol was further added as a stabilizer. The composition was heated to 80 ° C and subjected to a stability test. The stability test and the gelation were determined in the same manner as in Example 1. In the table, "○" means "ungelatinized", "X" means "gelation", and "-" means "not determined".

[Relationship between blending ratio of PE1 and TMP and preservation stability] Examples 15 to 18 and Comparative Examples 13 to 16:

The pentaerythritol tetrakis(3-hydroxythiobutyrate) (PE1) and trimethylolpropane trimethacrylate (lightester TMP, Kyoritsu Chemical Co., Ltd., C=C) were changed as shown in Table 4. Addition, mixing, and further, to the stabilizer, 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) at 40 ° C in a blending ratio of a double bond equivalent of 113 g/eq (TMP) Conduct a stability test. The stability test and the gelation were determined in the same manner as in Example 1. The results are shown in Table 4. In the table, "○" means "ungelatinized", "X" means "gelation", and "-" means "not determined".

Examples 19 to 21 and Comparative Examples 17 to 19:

As shown in Table 5, PE1 and TMPA were mixed while changing the blending ratio, and 4-methoxy-1-naphthol was further added as a stabilizer. The composition was heated to 80 ° C and subjected to a stability test. The results of measuring the initial viscosity after mixing of the composition and the viscosity after one day are shown in Table 5. The viscosity is an E-type rotational viscometer (Digital Rheometer type DV-III ULTRA, manufactured by BROOKFIELD), and a CP-41 cone sensor with a radius of 24 mm and an angle of 3° is used, and the number of rotations is 0.5 to 30 rpm (depending on the viscosity). Change), the viscosity at 25.0 ° C was measured. In the table, "X" means "gelation" and the value means "viscosity".

[Relationship between blending ratio of PE1 and TAIC and preservation stability] Examples 22 to 24 and Comparative Examples 20 to 22:

The pentaerythritol tetrakis(3-hydrothiobutyrate) (PE1) and triallyl isocyanurate (TAIC, manufactured by Tokyo Chemical Industry Co., Ltd., C=C double bond equivalent 83 g/) were changed as shown in Table 6. The blending ratio of eq) (TAIC) was added and mixed, and further, a stabilizer was added, and 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the stability test was carried out at 40 °C. The stability test and the gelation were determined in the same manner as in Example 1. The results are shown in Table 6. In the table, "○" means "ungelatinized", "X" means "gelation", and "-" means "not determined".

Examples 25 to 27 and Comparative Examples 23 to 25:

As shown in Table 7, the blending ratio was changed while PE1 and TAIC were mixed, and 4-methoxy-1-naphthol was added as a stabilizer. The composition was heated to 80 ° C and subjected to a stability test. The initial viscosity after mixing of the composition was measured and the viscosity after 14 days and 40 days. The viscosity is an E-type rotational viscometer (Digital Rheometer type DV-III ULTRA, manufactured by BROOKFIELD), and a CP-41 cone sensor with a radius of 24 mm and an angle of 3° is used, and the number of rotations is 0.5 to 30 rpm (depending on the viscosity). Change), the viscosity at 25.0 ° C was measured. In the table, the value means "viscosity".

[Industry use possibility]

The polyene-polythiol-based curable resin composition of the present invention has high sensitivity and excellent storage stability, and can be used in a printing plate or a color matching color proof, a color filter, a solder resist, and a light. Used in many applications such as hardening inks.

Claims (9)

A curable resin composition characterized by comprising: a thiol compound, a compound having an ethylenically unsaturated double bond having two or more unsaturated double bond groups, and a formula (1) (wherein R ⁵ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms; and at least 2 of R ⁵ to R ⁸ are a hydroxyl group or a compound represented by alkoxy group having 1 to 3 carbon atoms, wherein the total amount of the thiol group of the aforementioned thiol compound is relative to the total amount of the C=C double bond group of the compound containing an ethylenically unsaturated double bond. The ear ratio is 0.0001 to 1, and the content of the compound represented by the above formula (1) is from 1 to 20,000 wtppm based on the total mass of the thiol compound and the compound containing an ethylenically unsaturated double bond. The curable resin composition of claim 1, wherein R ⁵ to R ⁸ in the compound represented by the above formula (1) independently represent a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group, and R ⁵ At least two of ~R ⁸ are a hydroxyl group or a methoxy group. The curable resin composition according to claim 1 or 2, wherein the compound represented by the above formula (1) is 4-methoxy-1-naphthol, 1,4-Dimethoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-2-methyl-1-naphthol, 4-methoxy-3-methyl-1-naphthol, 1,4-Dimethoxy-2-methylnaphthalene, 1,2-dihydroxynaphthalene, 1,2-dihydroxy-4-methoxynaphthalene, 1,3-dihydroxy-4-methoxynaphthalene One or more selected from the group consisting of 1,4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, and 1,4-dihydroxy-2-methylnaphthalene Compound. The curable resin composition of claim 1, wherein the compound represented by the above formula (1) is 4-methoxy-1-naphthol. The curable resin composition of claim 1, wherein the thiol compound has two or more formula (2) (wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms, m is an integer of 0 to 2, and n is 0 or 1) a thiol compound based on the above, wherein the compound containing an ethylenically unsaturated double bond has two or more formula (3) (In the formula, R ³ and R ⁴ each independently represent a compound containing an ethylenically unsaturated double bond represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms). The curable resin composition of claim 5, wherein one of R ¹ and R ² in the group represented by the formula (2) represents an alkyl group having 1 to 10 carbon atoms, and the other represents A hydrogen atom. The sclerosing resin composition of claim 1, wherein the thiol compound is represented by the formula (4) An ester compound of a thiol group-containing carboxylic acid and a polyfunctional alcohol represented by the formula (wherein R ¹ , R ² , m and n are the same meanings as defined above). The sclerosing resin composition of claim 7, wherein the polyfunctional alcohol is an alkylene glycol having a branched carbon number of 2 to 10, diethylene glycol, dipropylene glycol, glycerin, or trishydroxyl Propane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, norbornyl dimethanol, 2,2-bis[4-(2-hydroxyethyloxy)phenyl]propane, hydrogenated bisphenol A selected compound of A, 4, 4'-(9-fluorenylene) bis(2-phenoxyethanol) and ginseng (2-hydroxyethyl) trimeric isocyanate. The curable resin composition of claim 5, wherein the compound having two or more groups represented by the above formula (3) and having an ethylenically unsaturated double bond is an acrylic group, a methacryl group, or the like. One or more compounds having a reactive double bond selected from a vinyl group and an allyl compound.