JP5647533B2 - Stabilized polyene-polythiol curable resin composition - Google Patents

Description

  The present invention relates to a polyene-polythiol-based photocurable resin composition with improved storage stability that can be used in fields such as printing plates, color proofs, color filters, solder resists, and photocurable inks.

  Photocurable resin compositions are used in various fields such as printing plates, color proofs, color filters, solder resists, and photocurable inks. Especially in recent years, from the viewpoints of environmental problems, energy saving, work safety, production cost, etc. including these applications, the most characteristic features of the photo-curable resin composition, such as room temperature curing, quick drying, no solvent, etc., have attracted attention. Many researches and developments have been made on compositions. In the development of color filters, pigment dispersion resists for color filters are being studied for the purpose of improving productivity and achieving high definition. In addition, color proofs and printing plates are being developed for the purpose of speeding up and increasing the precision of plate making. Also, solder resists for printed circuit boards are being studied.

  There is an increasing demand for photo-curing resin compositions in these applications, those that cure at lower energy, those that cure faster, those that can form finer patterns, those that have a deeper curing depth, and more storage High performance is required. The photocurable resin composition is mainly composed of a photopolymerization initiator composition, a compound having an ethylenically unsaturated bond that is cured by a polymerization reaction, and various additives. Used.

These photocurable compositions contain thiol compounds such as pentaerythritol tetrakis (3-mercapropionate) (trade name: QX40, manufactured by Mitsubishi Chemical Corporation) for reasons such as high sensitivity and high adhesion. It is used.
However, the photocurable resin composition using a thiol compound is highly sensitive, but has a problem that the storage stability is sacrificed because the reactivity is too high.

  JP 2010-024255 A (Patent Document 1) discloses an active energy ray-curable resin containing a urethane (meth) acrylate compound having three or more ethylenically unsaturated groups in its molecule, a thiol compound, and silica. Although the composition is described and shows that the coating film hardness and curability are excellent, the storage stability has not been studied.

  JP 2009-051936 A (Patent Document 2) discloses a curable composition containing a compound (A) obtained by reacting a diene compound and an organosilane compound containing a mercapto group and a thiol compound (B). Is disclosed, and it is described that a cured product having good curability and excellent storage stability is provided, but it is insufficient for obtaining long-term storage stability.

  Japanese Patent Application Laid-Open No. 2008-184514 (Patent Document 3) describes an ultraviolet curable resin composition containing a condensate obtained by hydrolysis and condensation of alkoxysilanes and a compound having a secondary thiol group. However, the storage stability was evaluated under mild conditions such as 30 days at room temperature, which was insufficient to obtain long-term storage stability at high temperatures.

  JP-A-8-504879 (Patent Document 4) discloses a thiol-ene composition having a stabilization system. As one of the options of the stabilization system, 4-methoxyphenol, hydroquinone, hydroquinone The use of a free radical scavenger such as a monoalkyl ester, benzoquinone, or naphthoquinone is described. Furthermore, although it is described that a suitable free radical scavenger is 4-methoxyphenol, in practical use, 4-methoxyphenol and naphthoquinone have a low stabilizing effect, and long-term storage stability at high temperatures. Can't get.

JP 2010-024255 A JP 2009-051936 A JP 2008-184514 A Japanese translation of PCT publication No. 8-504879

  An object of the present invention is to provide a photocurable resin composition that has high sensitivity, excellent storage stability, and can be used in a wide range of blending ratios of polyene and polythiol.

  As a result of intensive studies, the present inventors have obtained a photocurable resin composition containing a thiol compound, an ethylenically unsaturated double bond-containing compound, and a compound having a specific naphthalene skeleton as a stabilizer. While maintaining the high-sensitivity property at the time of photocuring, which is a characteristic of the polyene-polythiol-based photocurable resin composition, the ene-thiol reaction during storage is suppressed to prevent gelation, and good storage stability is obtained. The present invention has been completed.

（式中、Ｒ⁵〜Ｒ⁸は各々独立して、水素原子、炭素数１〜１０のアルキル基、ヒドロキシル基または炭素数１〜３のアルコキシ基を表し、Ｒ⁵〜Ｒ⁸のうち少なくとも２つはヒドロキシル基または炭素数１〜３のアルコキシ基である。）
で示される化合物を含有することを特徴とする硬化性樹脂組成物。
［２］ 前記一般式（１）で示される化合物中のＲ⁵〜Ｒ⁸が各々独立して、水素原子、メチル基、ヒドロキシル基またはメトキシ基を表し、Ｒ⁵〜Ｒ⁸のうち少なくとも２つがヒドロキシル基またはメトキシ基である前記［１］に記載の硬化性樹脂組成物。
［３］ 前記一般式（１）で示される化合物が、４−メトキシ−１−ナフトール、１，４−ジメトキシナフタレン、１，４−ジヒドロキシナフタレン、４−メトキシ−２−メチル−１−ナフトール、４−メトキシ−３−メチル−１−ナフトール、１，４−ジメトキシ−２−メチルナフタレン、１，２−ジヒドロキシナフタレン、１，２−ジヒドロキシ−４−メトキシナフタレン、１，３−ジヒドロキシ−４−メトキシナフタレン、１，４−ジヒドロキシ−２−メトキシナフタレン、１，４−ジメトキシ−２−ナフトール、及び１，４−ジヒドロキシ−２−メチルナフタレンから選ばれる、１種または２種以上の化合物である前記［１］または［２］に記載の硬化性樹脂組成物。
［４］ 前記一般式（１）で示される化合物が、４−メトキシ−１−ナフトールである前記［１］〜［３］のいずれかに記載の硬化性樹脂組成物。
［５］ 前記一般式（１）で示される化合物の含有量が、チオール化合物とエチレン性不飽和二重結合含有化合物の総質量に対して、１〜２００００ｗｔｐｐｍである前記［１］〜［４］のいずれかに記載の硬化性樹脂組成物。
［６］ 前記チオール化合物が一般式（２）

（式中、Ｒ¹及びＲ²は各々独立して、水素原子、炭素数１〜１０のアルキル基または炭素数６〜１０の芳香族基を表し、ｍは０〜２の整数であり、ｎは０または１である。）
で示される基を２個以上有するチオール化合物であり、前記エチレン性不飽和二重結合含有化合物が一般式（３）

（式中、Ｒ³及びＲ⁴は各々独立して、水素原子、炭素数１〜１０のアルキル基または炭素数６〜１０の芳香族基を表す。）
で示される基を２個以上有するエチレン性不飽和二重結合含有化合物である前記［１］〜［５］のいずれかに記載の硬化性樹脂組成物。
［７］ 前記一般式（２）で示される基中のＲ¹及びＲ²の一方が、炭素数１〜１０のアルキル基を表し、他方が水素原子を表す前記［６］に記載の硬化性樹脂組成物。
［８］ 前記チオール化合物が、一般式（４）

（式中、Ｒ¹、Ｒ²、ｍ、及びｎは上記と同義である。）
で示されるメルカプト基含有カルボン酸と多官能アルコールとのエステル化合物である前記［１］〜［７］のいずれかに記載の硬化性樹脂組成物。
［９］ 前記多官能アルコールが、分岐していてもよい炭素数２〜１０のアルキレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、シクロヘキサンジオール、シクロヘキサンジメタノール、ノルボルネンジメタノール、２，２−ビス[４−（２−ヒドロキシエチルオキシ）フェニル]プロパン、水素化ビスフェノールＡ、４，４’−（９−フルオレニリデン）ビス（２−フェノキシエタノール）及びトリス（２−ヒドロキシエチル）イソシアヌレートから選ばれる化合物である前記［８］に記載の硬化性樹脂組成物。
［１０］ 前記一般式（３）で示される基を２個以上有するエチレン性不飽和二重結合含有化合物が、アクリル、メタクリル、ビニル及びアリル化合物から選択される１種以上の反応性二重結合を有する化合物である前記［６］に記載の硬化性樹脂組成物。


That is, this invention relates to the polyene-polythiol type photocurable resin composition as described in the following [1]-[10].
[1] and a thiol compound, and an ethylenically unsaturated double bond group ethylenically unsaturated double bond-containing compound having two or more, the general formula (1)

(In the formula, R ^{5 to} R ⁸ each independently represents 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. Is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms.)
The curable resin composition characterized by containing the compound shown by these.
[2] R ^{5 to} R ⁸ in the compound represented by the general formula (1) each independently represent a hydrogen atom, a methyl group, a hydroxyl group, or a methoxy group, and at least two of R ^{5 to} R ⁸ are Curable resin composition as described in said [1] which is a hydroxyl group or a methoxy group.
[3] The compound represented by the general 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 1 or 2 or more compounds selected from 1,4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, and 1,4-dihydroxy-2-methylnaphthalene [1 Or the curable resin composition according to [2].
[4] The curable resin composition according to any one of [1] to [3], wherein the compound represented by the general formula (1) is 4-methoxy-1-naphthol.
[5] The above [1] to [4], wherein the content of the compound represented by the general formula (1) is 1 to 20000 wtppm with respect to the total mass of the thiol compound and the ethylenically unsaturated double bond-containing compound. The curable resin composition according to any one of the above.
[6] The thiol compound is represented by the general 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.)
And the ethylenically unsaturated double bond-containing compound is represented by the general formula (3):

(In the formula, 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 curable resin composition according to any one of [1] to [5], which is an ethylenically unsaturated double bond-containing compound having two or more groups represented by the formula:
[7] The curability according to [6], wherein ^one of R ¹ and R ^{2 in} the group represented by the general formula (2) represents an alkyl group having 1 to 10 carbon atoms, and the other represents a hydrogen atom. Resin composition.
[8] The thiol compound is represented by the general formula (4).

(In the formula, R ¹ , R ² , m, and n are as defined above.)
The curable resin composition according to any one of [1] to [7], which is an ester compound of a mercapto group-containing carboxylic acid and a polyfunctional alcohol represented by the formula (1).
[9] The C 2-10 alkylene glycol which may be branched, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, Norbornene dimethanol, 2,2-bis [4- (2-hydroxyethyloxy) phenyl] propane, hydrogenated bisphenol A, 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethanol) and tris (2-hydroxy The curable resin composition according to the above [8], which is a compound selected from ethyl) isocyanurate.
[10] One or more reactive double bonds in which the ethylenically unsaturated double bond-containing compound having two or more groups represented by the general formula (3) is selected from acrylic, methacrylic, vinyl, and allyl compounds The curable resin composition according to [6], wherein the curable resin composition is a compound having:

  The polyene-polythiol-based photocurable resin composition of the present invention has a very excellent storage stability, and a wide range of blends of polyenes and polythiols without inhibiting the reactivity of the composition even when a stabilizer is added. Since it can be used in a ratio, it is useful in various applications such as printing plates, color proofs, color filters, solder resists, and photocurable inks.

で示される基を２個以上有するチオール化合物である。 Hereinafter, the form for implementing this invention is demonstrated concretely.
The thiol compound used in the present invention is a compound having an —SH group, preferably a compound having 2 or more —SH groups, and more preferably a compound having 2 to 4 —SH groups.
Although the thiol compound used for this invention is not specifically limited, Preferably general formula (2)

A thiol compound having two or more groups represented by

In the general 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, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso -Butyl group, tert-butyl group, n-hexyl group, n-octyl group, etc. are mentioned, Preferably it is 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 toluyl group, a xylyl group, an ethylphenyl group, a 1,3,5-trimethylphenyl group, and a naphthyl group.

m represents an integer of 0 to 2, and is preferably 0 or 1.
n represents 0 or 1, and is preferably 0.
Further, m + n is preferably 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. Furthermore, from the viewpoint of adjusting photosensitivity and storage stability to a desired range, a secondary thiol compound in which ^one of R ¹ and R ² is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms is more preferable. preferable.

で示されるメルカプト基含有カルボン酸と多官能アルコールとのエステル化合物が好ましい。
上記一般式（４）中、Ｒ¹、Ｒ²、ｍ、及びｎは上記と同義である。 As a thiol compound used for this invention, general formula (4)

An ester compound of a mercapto group-containing carboxylic acid and a polyfunctional alcohol represented by
In said general formula (4), R < ¹ >, R < ² >, m, and n are synonymous with the above.

A polyfunctional alcohol is a compound having two or more hydroxyl groups.
Specific examples of the polyfunctional alcohol include 1,2-butanediol, diethylene glycol, dipropylene glycol and the like, optionally branched alkylene glycols having 2 to 10 carbon atoms, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol. , Cyclohexanediol, cyclohexanedimethanol, norbornenedimethanol, 2,2-bis [4- (2-hydroxyethyloxy) phenyl] propane, hydrogenated bisphenol A, 4,4 ′-(9-fluorenylidene) bis (2- Phenoxyethanol) and tris (2-hydroxyethyl) isocyanurate.

  A preferred polyfunctional alcohol is a bifunctional to tetrafunctional alcohol, more preferably 1,4-butanediol, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, or trimethylolpropane.

  Specific examples of the thiol compound used in the present invention include ethylene glycol bis (3-mercaptopropionate), 1,2-propylene glycol (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate). ), Ethylene glycol bis (3-mercaptobutyrate), 1,2-propylene glycol (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate) 1,2-propylene glycol bis (2-mercaptoisobutyrate) or trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3 − Lucaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,4-bis (3-mercaptobutyryloxy) butane, bisphenol A bis (3 -Mercaptopropionate), bisphenol A bis (3-mercaptobutyrate), triphenolmethanetris (3-mercaptopropionate), triphenolmethanetris (3-mercaptobutyrate). It is not limited to these. Pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) are easy to cure with a small exposure amount and have a large stability effect obtained by the present invention. ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,4-bis (3-mercaptobutyryloxy) butane can be preferably used.

  The thiol compound used in the present invention can also be easily obtained as a commercial product. The commercially available thiol compounds are pentaerythritol tetrakis (3-mercaptopropionate) (trade name: QX40, manufactured by Mitsubishi Chemical Corporation), trade name: QE-340M, manufactured by Toray Fine Chemical Co., Ltd., Ether-based primary thiol (trade name: Cup Cure 3-800, manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (trade name: Karenz MT BD1, manufactured by Showa Denko KK) ), Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1, manufactured by Showa Denko KK) is there.

で示される基を２個以上有するエチレン性不飽和二重結合含有化合物である。
上記一般式（３）中、Ｒ³及びＲ⁴は各々独立して、水素原子、炭素数１〜１０のアルキル基または炭素数６〜１０の芳香族基を表す。 The compound having an ethylenically unsaturated bond used in the present invention has the general formula (3)

It is an ethylenically unsaturated double bond containing compound which has 2 or more groups shown by these.
In the general 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, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso -Butyl group, tert-butyl group, n-hexyl group, n-octyl group, etc. are mentioned, Preferably it is a methyl group.

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

  The compound having an ethylenically unsaturated bond used in the present invention is generally called a monomer or oligomer and is a compound that can be cured by radical polymerization (or crosslinking) reaction. Specifically, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (Meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolethane di (meth) acrylate, tetramethylolethanetri (meth) acrylate, Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerystol di (meth) acrylate, dipentaerystol tri (meth) acrylate, dipentaerystol tetra (meth) acrylate, dipentaerystol penta (meth) acrylate, dipentaerystol hexa (meth) ) Acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate And (meth) acrylate of pentaerythritol triallyl ether, triallyl isocyanurate, bisphenol A alkylene oxide adduct, (meth) acrylate of triphenolmethane alkylene oxide adduct, etc., but the present invention is not limited thereto. It is not something. A polyfunctional (meth) acrylic monomer is preferred in view of exposure sensitivity and various resistances after curing. These compounds having an ethylenically unsaturated bond may be used alone or in combination of two or more. Note that “(meth) acrylate” means both “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 curable resin composition cannot be obtained.

で示される化合物を使用する。
上記一般式（１）中、Ｒ⁵〜Ｒ⁸は各々独立して、水素原子、炭素数１〜１０のアルキル基、ヒドロキシル基または炭素数１〜３のアルコキシ基を表す。 In the present invention, as the stabilizer, the general formula (1)

The compound shown by is used.
In said general formula (1), R < ⁵ > -R < ⁸ > represents a hydrogen atom, a C1-C10 alkyl group, a hydroxyl group, or a C1-C3 alkoxy group each independently.

The alkyl group having 1 to 10 carbon atoms represented by R ^{5 to} R ⁸ may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso group. -Butyl group, tert-butyl group, n-hexyl group, n-octyl group, etc. are mentioned, Preferably it is a methyl group.

Examples of the alkoxy group having 1 to 3 carbon atoms represented by R ^{5 to} R ⁸ include a methoxy group, an ethoxy group, a propoxy group, and an iso-propoxy group, and 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 two of R ^{5 to} R ⁸ are a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms. is there.

  As the compound represented by the general formula (1), a compound in which a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms is located at the 1,4-position, 2,3-position, or 1,2-position may have a radical resonance structure. This is preferable because it is possible. This is because the compound exhibits aromaticity and the stability of the compound alone is high. From the viewpoint of obtaining the compound, the substitution position is more preferably 1,4-position.

  Specific examples include 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, 1,4-dihydroxy-2-methoxy Examples include, but are not limited to, naphthalene, 1,4-dimethoxy-2-naphthol, and 1,4-dihydroxy-2-methylnaphthalene. Among these, 4-methoxy-1-naphthol and 1,4-dihydroxynaphthalene are more preferable from the viewpoint of storage stability and reactivity of the composition.

  The blending ratio of the thiol compound and the ethylenically unsaturated double bond-containing compound is not particularly limited, but the total amount of thiol groups of the thiol compound with respect to the total amount of C = C double bond groups of the ethylenically unsaturated double bond-containing compound. The molar ratio is preferably 0.0001 to 1, more preferably 0.001 to 0.5, and still more preferably 0.01 to 0.1.

  The amount of the stabilizer is preferably 1 to 20000 wtppm, more preferably 10 to 10000 wtppm, and still more preferably 50 to 5000 wtppm with respect to the total mass of the thiol compound and the ethylenically unsaturated double bond-containing compound. In the case of a secondary or tertiary thiol compound that is less reactive than the primary thiol compound, 1 to 2000 wtppm is preferred, 10 to 1000 wtppm is more preferred, and 50 to 500 wtppm is even more preferred. Moreover, in the case of a primary thiol compound, 10-20000 wtppm is preferable, 100-10000 wtppm is more preferable, 500-5000 wtppm is further more preferable. If the amount of the stabilizer is less than 1 wtppm, the stabilizing effect is insufficient and gelation occurs during storage, and if the amount of the stabilizer is more than 20000 wtppm, the curability during photocuring tends to deteriorate.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and the curable resin composition of this invention is demonstrated, this invention is not limited to the following examples.

[Storage stability test]
Example 1:
Pentaerythritol tetrakis (3-mercaptobutyrate) (PE1, Showa Denko KK, SH equivalent 139 g / eq) 5.9 g, trimethylolpropane triacrylate (Light acrylate TMPA, manufactured by Kyoeisha Chemical Co., Ltd.), C = C double bond equivalent 99 g / eq) 4.1 g so that the molar ratio of the thiol group of the thiol compound is 1 with respect to the total amount of C═C double bond groups of the ethylenically unsaturated double bond-containing compound. Mixed. Furthermore, 0.02 g (2000 wtppm) of 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a stabilizer. When this composition was heated to 60 ° C. and the number of days until gelation was measured, it did not gel for 120 days.
The determination method for gelation was determined to be gelation when the stored bottle was tilted and the deposit was visually observed.

Example 2:
When the same stability test as in Example 1 was performed except that 0.003 g (300 wtppm) of 4-methoxy-1-naphthol was used, gelation did not occur for 90 days or more.

Example 3:
The same stability test as in Example 1 was conducted except that 0.02 g (2000 wtppm) of 1,4-dihydroxynaphthalene was used instead of using 4-methoxy-1-naphthol. There wasn't.

Comparative Examples 1-8:
Instead of 4-methoxy-1-naphthol, 2,2′-methylenebis (6-tert-butyl-p-cresol) (Comparative Example 1) shown in Table 1 as a stabilizer, 2,6-di-tert- Butyl-4-hydroxytoluene (Comparative Example 2), 4-methoxyphenol (Comparative Example 3), methylhydroquinone (Comparative Example 4), phenothiazine (Comparative Example 5), N-nitrosophenylhydroxylamine ammonium salt (Comparative Example 6) And 2,2,6,6-tetramethylpiperidine-1-oxyl (Comparative Example 7) or 0.02 g (2000 wtppm) is added, or no stabilizer is used (Comparative Example 8). The stability test similar to 1 was performed. The results are shown in Table 1. In the table, “◯” means “not gelled”, “x” means “gelled”, and “−” means “not measured”.

[Measurement of acrylic reaction rate]
Example 4:
5.9 g of pentaerythritol tetrakis (3-mercaptobutyrate) (PE1) and 4.1 g of trimethylolpropane triacrylate (TMPA) are added to the total amount of C═C double bond groups of the ethylenically unsaturated double bond-containing compound. On the other hand, mixing was performed so that the molar ratio of the total amount of thiol groups of the thiol compound was 1. As a stabilizer, 0.003 g (300 wtppm) of 4-methoxy-1-naphthol was added. Further, 0.1 g of IRG184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added as a radical initiator. This was applied to a NaCl plate with a film thickness of 30 μm, and an exposure amount of 360 mJ / cm ^{2 was} irradiated to form a film. The acrylic reaction rate of the film was measured. The measuring method used FT-IR and measured the acrylic reaction rate by the area change rate of 810 cm < ^-1 > which is the peak of an acrylic group. As a result, the acrylic reaction rate was 94%.

Comparative Example 9:
The acrylic reaction rate was measured by the same method except that 4-methoxy-1-naphthol of Example 4 was not added. As a result, the acrylic reaction rate was 92%, which was the same as in Example 4.

[Relationship between blending ratio of PE1 and TMPA and storage stability]
Examples 5-11:
As shown in Table 2, PE1 and TMPA were mixed at different blending ratios, and 4-methoxy-1-naphthol was added as a stabilizer, and a stability test was performed at 40 ° C. The stability test and gelation determination were performed in the same manner as in Example 1. The results are shown in Table 2. In the table, “◯” means “not gelled”, “x” means “gelled”, and “−” means “not measured”.

Examples 12-14, Comparative Examples 10-12:
As shown in Table 3, PE1 and TMPA were mixed at different blending ratios, and 4-methoxy-1-naphthol was added as a stabilizer. This composition was heated to 80 ° C. and the number of days until gelation was measured. In the table, “◯” means “not gelled”, “x” means “gelled”, and “−” means “not measured”. The gelation was determined in the same manner as in Example 1.

[Relationship between blending ratio of PE1 and TMP and storage stability]
Examples 15-18, Comparative Examples 13-16:
As shown in Table 4, pentaerythritol tetrakis (3-mercaptobutyrate) (PE1) and trimethylolpropane trimethacrylate (light ester TMP, manufactured by Kyoeisha Chemical Co., Ltd., C = C double bond equivalent 113 g / eq) (TMP) is added and mixed while changing the blending ratio, and 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a stabilizer, and the stability test is conducted at 40 ° C. went. The stability test and gelation determination were performed in the same manner as in Example 1. The results are shown in Table 4. In the table, “◯” means “not gelled”, “x” means “gelled”, and “−” means “not measured”.

Examples 19-21, Comparative Examples 17-19:
As shown in Table 5, PE1 and TMP were mixed at different blending ratios, and 4-methoxy-1-naphthol was added as a stabilizer. This composition was heated to 80 ° C. and subjected to a stability test. Table 5 shows the results of measuring the initial viscosity immediately after mixing the composition and the viscosity after one day. Viscosity was measured using an E-type rotational viscometer (digital rheometer model DV-III ULTRA, manufactured by BROOKFIELD) and a rotational speed of 0.5 to 30 rpm using a CP-41 type cone plate type sensor having a radius of 24 mm and an angle of 3 °. Viscosity at 25.0 ° C. was measured. In the table, “x” means “gelation” and the numerical value means “viscosity”.

[Relationship between blending ratio of PE1 and TAIC and storage stability]
Examples 22-24, Comparative Examples 20-22:
As shown in Table 6, pentaerythritol tetrakis (3-mercaptobutyrate) (PE1) and triallyl isocyanurate (TAIC, manufactured by Tokyo Chemical Industry Co., Ltd., C = C double bond equivalent 83 g / eq) (TAIC ) Was added and mixed, and 4-methoxy-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added as a stabilizer, and a stability test was conducted at 40 ° C. The stability test and gelation determination were performed in the same manner as in Example 1. The results are shown in Table 6. In the table, “◯” means “not gelled”, “x” means “gelled”, and “−” means “not measured”.

Examples 25-27, Comparative Examples 23-25:
As shown in Table 7, PE1 and TAIC were mixed at different blending ratios, and 4-methoxy-1-naphthol was added as a stabilizer. This composition was heated to 80 ° C. and subjected to a stability test. The initial viscosity immediately after mixing the composition and the viscosity after 14 and 40 days were measured. Viscosity was measured using an E-type rotational viscometer (digital rheometer model DV-III ULTRA, manufactured by BROOKFIELD) and a rotational speed of 0.5 to 30 rpm using a CP-41 type cone plate type sensor having a radius of 24 mm and an angle of 3 °. Viscosity at 25.0 ° C. was measured. In the table, the numerical value means “viscosity”.

  The polyene-polythiol-based photocurable resin composition of the present invention has high sensitivity and very excellent storage stability, and is used in various fields such as printing plates, color proofs, color filters, solder resists, and photocurable inks. Useful in applications.

Claims (10)

A thiol compound, an ethylenically unsaturated double bond-containing compound an ethylenically unsaturated double bond group having 2 or more, the general formula (1)

(In the formula, R ^{5 to} R ⁸ each independently represents 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. Is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms.)
The curable resin composition characterized by containing the compound shown by these. R ^{5 to} R ⁸ in the compound represented by the general formula (1) each independently represents a hydrogen atom, a methyl group, a hydroxyl group or a methoxy group, and at least two of R ^{5 to} R ⁸ are a hydroxyl group or The curable resin composition according to claim 1, which is a methoxy group.   The compound represented by the general 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, 1, The compound according to claim 1 or 2, which is one or more compounds selected from 4-dihydroxy-2-methoxynaphthalene, 1,4-dimethoxy-2-naphthol, and 1,4-dihydroxy-2-methylnaphthalene. The curable resin composition described.   The curable resin composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is 4-methoxy-1-naphthol.   5. The content of the compound represented by the general formula (1) is 1 to 20000 wtppm with respect to the total mass of the thiol compound and the ethylenically unsaturated double bond-containing compound. Curable resin composition. The thiol compound is represented by the general 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.)
And the ethylenically unsaturated double bond-containing compound is represented by the general formula (3):

(In the formula, 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 curable resin composition according to claim 1, which is an ethylenically unsaturated double bond-containing compound having two or more groups represented by the formula: The curable resin composition according to claim 6, wherein ^one of R ¹ and R ^{2 in} the group represented by the general formula (2) represents an alkyl group having 1 to 10 carbon atoms, and the other represents a hydrogen atom. The thiol compound has the general formula (4)

(In the formula, R ¹ , R ² , m, and n are as defined above.)
The curable resin composition according to any one of claims 1 to 7, which is an ester compound of a mercapto group-containing carboxylic acid and a polyfunctional alcohol.   The polyfunctional alcohol may be branched alkylene having 2 to 10 carbon atoms, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, cyclohexanediol, cyclohexanedimethanol, norbornene dimethanol 2,2-bis [4- (2-hydroxyethyloxy) phenyl] propane, hydrogenated bisphenol A, 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethanol) and tris (2-hydroxyethyl) isocyanate The curable resin composition according to claim 8, which is a compound selected from nurate.   The compound in which the ethylenically unsaturated double bond-containing compound having two or more groups represented by the general formula (3) has one or more reactive double bonds selected from acrylic, methacrylic, vinyl and allyl compounds The curable resin composition according to claim 6.