JP2013237750A - Light thiol generator, and photosensitive resin composition containing the light thiol generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a light thiol generator in which reaction efficiency is excellent and practicality is high, that is excellent in storage stability even if being used as a radiation curing material, and in which carbon dioxide gas does not occur at thiol generation; and a photosensitive resin composition that contains the light thiol generator.SOLUTION: In a light thiol generator, since photocyclization reaction is caused by irradiation of light and thiol is generated, progress of the reaction can be controlled by the irradiation of light. Moreover, a group of an α position of a carbonyl group adjacent to an S group does not become a hydrogen atom. By presence of such group, even if the light thiol generator is used to be combined with a thiol reaction compound as a radiation curing material, pot life is long, storage stability is excellent, reaction efficiency is excellent, and practicality is high. Thus a carboxylic acid compound is produced in which generation of carbon dioxide gas does not occur at generation of thiol.

Description

  The present invention relates to a photothiol generator and a photosensitive resin composition containing the photothiol generator. More specifically, the present invention relates to a photothiol generator that generates thiol by active energy rays such as light and a photosensitive resin composition containing the photothiol generator.

  It is known that a resin composition containing a sulfur atom exhibits a high refractive index and has excellent transparency. Since the thiol group represented by —SH has high reactivity with various functional groups such as an epoxy group, it is a functional group that can be used as a curing functional group of the curable resin composition, Various thiol compounds containing such a thiol group are provided (see, for example, Patent Document 1 or Patent Document 2).

  However, since the thiol group has high reactivity, when the thiol compound and the epoxy compound are mixed, the curing reaction proceeds too much and the viscosity becomes too high. In addition, compounds containing thiol groups are known to form disulfide bonds when thiol groups react with each other, but the reactivity of the thiol groups is high, making it difficult to control the reaction. It has been difficult to obtain a curable resin composition having storage stability (storage stability).

  In addition, UV curable materials using radical polymerization occupy most of the UV curable materials in practical use, but there is a problem that they are significantly affected by polymerization inhibition (oxygen inhibition) in which polymerization is stopped by oxygen in the air. It was. As a technique for solving this problem, use of a thiol-ene reaction has been proposed.

  The thiol-ene reaction (also referred to as ene-thiol reaction) that occurs by irradiating thiol and olefin with light can be reacted without using a photopolymerization initiator, is less susceptible to oxygen inhibition, and has little cure shrinkage. It is a very useful reaction. On the other hand, when an acrylic monomer or methacrylic monomer and a thiol compound are mixed, the polymerization gradually proceeds to increase the viscosity, so that storage stability is also a problem here, and the acrylic monomer and the thiol compound are reacted. In some cases, it was necessary to mix the two before use.

  Therefore, development of a photothiol generator (PTG) that generates thiol by light irradiation is required, and a photosensitive resin composition containing a photothiol generator that generates thiol by light irradiation is a photoresist material or It is applied as a photo-curing material or the like (see, for example, Patent Document 3).

JP 2006-154774 A International Publication WO2007 / 084661 Pamphlet JP 2007-241144 A

However, the conventionally provided photothiol generators have problems such as the fact that the reaction of generating thiols by the action of light is not performed rapidly, and thus are not practical and have been required to be improved. In addition, the conventional photothiol generator was accompanied by the generation of carbon dioxide (CO ₂ ) as a decomposition product when generating thiol, but such carbon dioxide is used when a photosensitive resin composition is formed into a film. In that case, bubbles were formed, which was a cause of unevenness in the cured film. Here, in the case where the photosensitive resin composition is formed, if bubbles remain in the cured film, the strength of the cured film is reduced, and when used as an adhesive, the adhesive strength is reduced. In the case of using it as a stopping material or a coating material, problems such as deterioration of barrier properties against impurities in the air such as water and thiol compounds occur, which is not preferable.

  The present invention has been made in view of the above-mentioned problems, and has good reaction efficiency and high practicality, is excellent in storage stability even when used as a photocuring material, and does not generate carbon dioxide when thiol is generated. The object is to provide a photothiol generator and a photosensitive resin composition containing the photothiol generator.

  In order to solve the above-mentioned problems, the photothiol generator according to the first invention of the present invention is represented by the following formula (X).

(In Formula (X), R ₁ is an organic group, which may be a linear structure, a branched structure, or a cyclic structure, and may contain a hetero atom. Further, R ₁ includes a silyl group, an acryl group, and a methacryl group. R ₂ may be a halogen, a hydroxyl group, a sulfide group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, or a sulfonate group. Group, phosphino group, phosphinyl group, phosphono group, phosphonato group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group, alkoxy group, amino group, amide group, aryl group, allyl group, or organic group R ₃ is a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, Rufo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group, alkoxy group, amino group, amide group, aryl group, allyl group Furthermore, R ₂ and R ₃ may contain a polymerizable group such as a silyl group, an acryl group, or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them. ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, Phosphono group, phosphonato group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group Alkoxy group, an amino group, an amide group, an aryl group, an allyl group, an ammonio group or an organic group, and may be be the same or different. Furthermore, the R _{4, R 5,} R ₆ and R ₇ , A silyl group, an acryl group, a methacryl group, or a monomer or a polymer obtained by polymerizing them, and R ₄ , R ₅ , R ₆ and R ₇ are those represented by 2 Two or more may be bonded to form a cyclic structure, and may include a heteroatom bond.)

  The photothiol generator according to the second aspect of the present invention is represented by the following formula (Xa).

(In the formula (Xa), l and m are integers of 0 to 8, n is an integer of 1 to 6, Y is a tetravalent carbon, aromatic ring, triazine ring, or organic group, and the organic group is straight It may be a chain structure, a branched structure, or a cyclic structure, and may contain a heteroatom, and Y may contain a polymerizable group such as a silyl group, an acryl group, or a methacryl group, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same as those in the above formula (X), and R ₈ is an ester group or amide which is a functional group. And represents oxygen, sulfur which is a group, amino group, carbonyl group, alkyl group, or hetero atom.)

In the photothiol generator according to the present invention, in the first invention or the second invention, the R ₂ is an alkyl group having 1 to 12 carbon atoms, and the R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is a hydrogen atom.

  The photosensitive resin composition according to the present invention includes the above-described photothiol generator of the present invention and a thiol-reactive compound.

  In the photosensitive resin composition according to the present invention, in the above-described present invention, the thiol-reactive compound is at least one selected from the group consisting of an epoxy compound, an episulfide compound, an acrylic compound, a methacrylic compound and a maleimide compound. It is a seed.

  Since the photothiol generator according to the present invention generates a thiol by generating a photocyclization reaction by light irradiation, the progress of the reaction can be controlled by light irradiation, so it is used as a photo-curing material in combination with a thiol-reactive compound Even so, the carboxylic acid compound has a long pot life, excellent storage stability, good reaction efficiency, high practicality, and no generation of carbon dioxide when thiol is generated.

  Since the photosensitive resin composition according to the present invention contains the photothiol generator of the present invention and a thiol reactive compound, the reaction between the thiol generated from the photothiol generator and a thiol reactive compound such as an epoxy compound. Thus, the curing is sufficiently performed. In addition, since the added photothiol generator does not generate carbon dioxide when thiol is generated, it does not cause unevenness due to carbon dioxide bubbles in the cured film, and a cured film with high product characteristics and product value can be obtained. Can be provided. And since progress of reaction can be controlled by irradiation of light, even if it uses as a photocuring material, it becomes a photosensitive resin composition which has a long pot life and is excellent in storage stability.

It is the figure which showed the solubility with respect to the organic solvent of a photothiol generator. It is the figure which compared the photodegradation behavior in wavelength 254nm light in the photothiol generator of Example 2 thru | or Example 5. It is the figure which compared the photolysis behavior in wavelength 313nm light in the photothiol generator of Example 2 thru | or Example 5. It is the figure which compared the photolysis behavior in wavelength 365nm light in the photothiol generator of Example 2 thru | or Example 5. It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate) of the photosensitive resin composition obtained in Example 6. It is the figure which showed the sensitivity evaluation result (relationship between exposure amount and remaining film rate) of the photosensitive resin composition obtained in Example 7. It is the figure which showed the relationship between the exposure amount in Test Example 10, and pencil hardness. It is the figure which showed the relationship between the exposure amount and the pencil hardness in Test Example 11. It is the figure which compared the relationship between the exposure amount of the photosensitive resin composition of Example 8 and Example 9, and a residual film rate. It is the figure which showed the relationship between addition amount and the transmittance | permeability about the cured film obtained by light irradiation. 14 is a view showing an appearance photograph of a microtube in Test Example 12. FIG. It is the figure (what does not add the photoinitiator) which showed the relationship between the exposure amount in the test example 13, and pencil hardness. It is the figure (what added the photoinitiator) which showed the relationship between the exposure amount and the pencil hardness in Test Example 13. It is the figure which showed the relationship between the exposure amount and the pencil hardness in Test Example 14. It is the figure which showed the relationship between the exposure amount and the change rate of the peak (810 cm < ^-1 >) area of C = C.

  Hereinafter, one embodiment of the present invention will be described. The photothiol generator according to the present invention is a compound represented by the following formula (X).

In formula (X), R ₁ is an organic group, which may have a linear structure, a branched structure, or a cyclic structure, and may contain a hetero atom. Furthermore, R ₁ may contain a polymerizable group such as a silyl group, an acrylic group, or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them.

There is no restriction | limiting in particular as an organic group, Although a conventionally well-known organic group can be used, For example, C1-C20 alkyl group (preferably C1-C12 alkyl group), C2-C2 Examples include 12 alkenyl groups, alkynyl groups, and aromatic groups having 6 to 12 carbon atoms. Such organic group, _(R 2 _{~R 7} of and formula (X-a)) organic group constituting Y below _R 2 to R ₇ and below for formula (X-a) are also common.

  The organic group may have a linear structure, a branched structure, or a cyclic structure. Examples of the linear structure include methyl, ethyl, propyl, butyl, pentyl and the like. As carbon number of a linear structure, 1-12 are preferable and C1-C6 is especially preferable.

  Examples of the branched structure include a branched alkyl group having 3 to 12 carbon atoms, specifically, i-propyl group, i-butyl group, s-butyl group, t-butyl group, An isopentyl group, neopentyl group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like are preferable. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are more preferable, and i-propyl group, s-butyl group, t-butyl group and the like are particularly preferable.

  Examples of the cyclic structure include an alicyclic hydrocarbon group having 5 to 20 carbon atoms, specifically, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, An adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like, and groups having these are preferable. Among these, dicyclopentenyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group and the like are more preferable, dicyclopentenyl group, cyclohexyl group, norbornyl Group, isobornyl group, tricyclopentenyl group and the like are more preferable, and dicyclopentenyl group and tricyclopentenyl group are particularly preferable.

R ₂ is halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, carboxyl group, carbonyl group, ester group, A formyl group, an acyl group, a cyano group, an alkoxy group, an amino group, an amide group, an aryl group, an allyl group, or an organic group.

R ₃ is a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, carboxyl group, carbonyl group, ester Group, formyl group, acyl group, cyano group, alkoxy group, amino group, amide group, aryl group, allyl group, or organic group, which may be the same or different. Furthermore, R ₂ and R ₃ may contain a polymerizable group such as a silyl group, an acryl group, or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them.

R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group , Phosphono group, phosphonate group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group, alkoxy group, amino group, amide group, aryl group, allyl group, ammonio group, or organic group, the same Or different. Furthermore, R ₄ , R ₅ , R ₆ and R ₇ may contain a polymerizable group such as a silyl group, an acryl group or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them. . Two or more of R ₄ , R ₅ , R ₆ and R ₇ may be bonded to form a cyclic structure, and may include a hetero atom bond.

In the formula (X), R ₂ may be an alkyl group having 1 to 12 carbon atoms, and R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be hydrogen atoms.

  Further, the photothiol generator of the present invention may be as shown in (Xa) below.

  In the formula (Xa), l and m are integers of 0 to 8, n is an integer of 1 to 6, and Y is a tetravalent carbon, aromatic ring, triazine ring, or organic group. l is preferably 1 to 3, and m is preferably 1 to 3.

The organic group for Y may have a straight chain structure, a branched structure, or a cyclic structure, and may contain a hetero atom. Furthermore, Y may contain a polymerizable group such as a silyl group, an acryl group or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are in common with the formula (X) described above.

In the photothiol generator of the present invention, in the structures of the formulas (X) and (Xa), the R ₂ group at the α-position of the carbonyl group adjacent to the S group is not a hydrogen atom, but the above-described group. . Due to the presence of such groups, thiols are generated by light irradiation. On the other hand, if such an R ₂ group does not exist (when it becomes a hydrogen atom), the cyclization reaction proceeds and thiols are generated without irradiation with light, which is thermally unstable and combined with a curable material. It is inferior in storage stability when used.)

R ₈ may be a functional group such as an ester group, an amide group, an amino group, a carbonyl group, an alkyl group, or a hetero atom such as oxygen or sulfur.

In the formula (Xa), the number n of the portion bonded to the Y group shown in the following (Xa ′) is determined by the valence of the Y group (the number that can be bonded to other groups). For example, when Y is tetravalent carbon, n = 4, when aromatic, n = 1 to 6, and when triazine rings such as 1,3,5-triazine-2,4,6-trione, n = 3. n is determined in the case of alkylene which is an organic group, n = 2, and n = 6 in the case of a compound of the following formula (A) which is an organic group. The part which couple | bonds with Y group may be made to have a common structure, when two or more couple | bonds with Y. Similarly to the above formula (X), R ₂ may be an alkyl group having 1 to 12 carbon atoms, and R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be hydrogen atoms.

  In the photothiol generator of the present invention, as shown in the following scheme, a carboxylic acid derivative undergoes a photocyclization reaction by light irradiation to generate thiol (-SH). Since the photothiol generator according to the present invention generates thiol by photocyclization reaction of a carboxylic acid derivative by light irradiation as shown in Scheme 1, the progress of the reaction can be controlled by light irradiation. Even if it is used as a photo-curing material in combination with a functional compound, it becomes a thiol compound having a long pot life and excellent storage stability. In the following scheme 1, the structure of the photothiol generator is simplified.

(Scheme 1)

The photothiol generator of the present invention does not generate carbon dioxide (CO ₂ ) as a decomposition product when generating thiols. Such carbon dioxide gas becomes bubbles when the photosensitive resin composition is formed, and the cured film has irregularities, and the strength of the cured film is lowered. However, when the photothiol generator according to the present invention was applied to a thiol-reactive compound such as an epoxy compound, the reaction efficiency was good and the carbon dioxide gas It is possible to provide a cured film having no product characteristics and product value. In addition, coumarin (coumarin compound) is produced as a by-product by the reaction, but since such coumarin is radically polymerizable and also susceptible to Michael addition reaction, a thiol / epoxy compound-based or thiol-ene-based composition. Will be taken in.

  In order to produce the photothiol generator represented by the formula (X), for example, it can be produced according to the following synthesis scheme. The scheme of formula (X) is shown as an example, but the synthesis is basically a reaction between a polyfunctional thiol and a carboxylic acid, and only the polyfunctionality of the thiol is different. The steps are all the same.

(Synthesis scheme)

  Hereinafter, the photothiol generator of the present invention corresponding to Formula (X) is represented by Formula (X-1), and the photothiol generator of the present invention corresponding to Formula (Xa) is represented by Formula (X-2), Formula (X-3), Formula (X-4), Formula (X-5) and Formula (X-6) are shown respectively.

The photothiol generator of the present invention, and the range of the irradiation light wavelength and exposure amount in the photosensitive resin composition containing the photothiol generator, the type and amount of the photothiol generator, and the photosensitive resin composition May be appropriately determined according to the type of the thiol-reactive compound constituting, for example, within the range of 190 to 400 nm as the wavelength and 100 to 30000 mJ / cm ² (preferably 100 to 10000 mJ / cm ² ) as the exposure amount. The long wavelength region can be used by using a sensitizer described later. Although irradiation time of irradiation light may be possible even for several seconds, it may be about 10 seconds or more, and is preferably 1.5 to 60 minutes.

  Next, the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention contains the above-mentioned photothiol generator that generates a thiol by causing a photocyclization reaction by light irradiation and a thiol-reactive compound as essential components.

  The thiol-reactive compound constituting the photosensitive resin composition of the present invention is not particularly limited as long as it is a compound that reacts by the action of a thiol generated by a photothiol generator and cures by crosslinking or the like. A compound, an episulfide compound, an acrylic compound, a methacrylic compound, a maleimide compound, or the like can be used. Further, a resin or compound having a group (C≡C group) having a carbon-carbon triple bond may be used. One of these thiol-reactive compounds may be used alone, or two or more of them may be used in combination. Moreover, the photothiol generator contained in the photosensitive resin composition may be used alone or in combination of two or more.

  Of the thiol-reactive compounds described above, epoxy compounds, episulfide compounds, and the like are cured by ionic reaction with thiols. In addition, acrylic compounds, methacrylic compounds, maleimide compounds, and the like are cured by radical reaction (thiol-ene reaction) with thiols.

A reaction scheme of an epoxy compound, an episulfide compound and the like with a photothiol generator is shown below. The generated thiol reacts with an epoxy compound and the like to generate a three-dimensional cross-linked network. In the following scheme, R and R ₂ are arbitrary organic groups, and n is an arbitrary integer of 1 or more.

(Reaction scheme)

  In addition, a general thiol-ene reaction is formed by the following initiation reaction, growth reaction, termination reaction, and reaction with oxygen. The generated thiyl radical reacts with a thiol-reactive compound to form a three-dimensional body (Cross- linked networks). Here, I · represents a radical active species generated by decomposition of a photoinitiator, and M represents a monomer or a polymer thereof. R is an arbitrary organic group.

(Initiation reaction, growth reaction)

(Stop reaction)

(Reaction with oxygen (O ₂ ))

  Hereinafter, an example of the thiol reactive compound which can be used for the photosensitive resin composition concerning this invention is given. These thiol-reactive compounds may be synthesized by a conventional method, or commercially available products may be used.

  The epoxy compound is not particularly limited as long as it has one or more epoxy groups in the molecule, and conventionally known compounds can be used. Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Polyfunctional epoxy resins such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin, There are lysidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc. These epoxy resins may be halogenated and hydrogenated. It may be. As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Industries, Ltd., Eporide series, EHPE Series, YD series, YDF series, YDFN series, YDB series by Toto Kasei Co., Ltd., Denacol series by Nagase ChemteX, Epolite series by Kyoeisha Chemical Co., Ltd. Although's etc. but the invention is not limited thereto. Two or more of these epoxy resins may be used in combination. Among these, bisphenol-type epoxy resins are preferable because grades having different molecular weights are widely available as compared with other various epoxy compounds, and adhesiveness and reactivity can be arbitrarily set.

  When using a compound having one or more epoxy groups in the molecule or a polymer having two or more epoxy groups in the molecule (epoxy resin), 2 functional groups having reactivity with the epoxy group are present in the molecule. Two or more compounds may be used in combination. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.

  Moreover, it is preferable to use what introduce | transduced the said functional group into the polymer side chain of weight average molecular weight 3,000-100,000. If it is less than 3,000, the film strength is lowered and tackiness occurs on the surface of the cured film, and impurities and the like are likely to adhere. On the other hand, if it exceeds 100,000, the viscosity may increase, which is not preferable.

  Other usable epoxy compounds include, for example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol polyglycidyl ether, Diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ester Tellurium, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether, glycidyl Examples include propoxytrimethoxysilane. These epoxy compounds may be halogenated or hydrogenated, and these epoxy compounds include derivatives. And these epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Also, polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl An epoxy group-containing polymer of a methacrylate copolymer may be used. These epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the episulfide compound, a compound having two or more episulfide groups in the molecule is preferably used. For example, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide Bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, 1, 3-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) ) Butane, 1,4-bis (2,3-epithiopropylthio) -2-methylbutane, 1,3-bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3- D Thiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio) -2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6 -Bis (2,3-epithiopropylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3-epithiopropylthio) -1,3-bis (2, 3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3 -Epithiopropylthio) -2- (2 3-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3-epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epithiopropylthio) ) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl)- 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio E) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,5-bis (2, 3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl)- 3,6-dithiaoctane, 1,1,1-tris [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] -2- (2,3-epithiopropylthio) ethane, 1,1, 2,2-tetrakis [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3 -Epithiopropylthiomethyl) -3,6,9-tri Aundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis Chain aliphatic 2,3-epithio such as (2,3-epithiopropylthio) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane Propylthio compounds, 1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3- Epithiopropylthiomethyl) cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2 , 5- [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl-1 Cycloaliphatic 2,3-epithiopropylthio compounds such as 1,4-dithiane, 1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epi Thiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene, 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3 -Epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropylthiomethyl) benzene, bis {4- (2,3-epithiopropylthio) phenyl} methane, 2,2-bis {4- (2,3-epithiop Ropylthio) phenyl} propane, bis {4- (2,3-epithiopropylthio) phenyl} sulfide, bis {4- (2,3-epithiopropylthio) phenyl} sulfone, 4,4′-bis (2 , 3-epithiopropylthio) biphenyl, and the like. One of these episulfide compounds may be used alone, or two or more thereof may be used in combination.

  The maleimide compound is a compound having a maleimide structure in the molecular structure, and a compound having two or more maleimide structures in one molecule (for example, a bismaleimide compound) is preferably used. Examples of the bismaleimide compound having two or more maleimide structures in one molecule include 1-methyl-2,4-bismaleimide benzene, N, N′-m-phenylenebismaleimide, N, N′-p. -Phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'-4,4 '-[3,3'-dimethyl-biphenylene Bismaleimide, N, N′-4,4 ′-[3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4,4′-diphenyl ether bismale N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-4- (4-maleimidophenoxy) phenyl] propane, 1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) -5-t-butylphenyl] -2-methylpropane, 4, 4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-ma Imidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene], 4,4′-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′ -(1-Methylethylidene) -bis [1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 '-(2-ethylhexylidene) -bis [1 -(Maleimidophenoxy) -benzene], 4,4 '-(1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4'-cyclohexylidene-bi [1- (maleimidophenoxy) -3-methylbenzene], 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4- Maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) ) Phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl ] Propane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [3 Methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8- Bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2. 1.02,6] decane, 3,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 4,9-bis [4- (4- Maleimidophenoxy) phenyl] -tricyclo [5.2.1.02,6] decane, 1,8-bis [4- (4-maleimidophenoxy) phenyl] menthane, 1,8-bi [3-methyl-4- (4-maleimide phenoxy) phenyl] menthane, 1,8-bis [3,5-dimethyl-4- (4-maleimide phenoxy) phenyl] menthane and the like. These maleimide compounds may be used alone or in combination of two or more. Of these maleimide compounds, it is preferable to use a compound having no halogen atom in the molecule from the viewpoint of further suppressing the generation of harmful substances. The maleimide compound may be used alone, but is preferably used in combination with other thiol-reactive compounds.

  Examples of acrylic compounds and methacrylic compounds include pentaerythritol triacrylate, pentaerythritol tetraacrylate, acrylic modified alkyd, methacryl modified alkyd, epoxy acrylate, epoxy methacrylate, urethane acrylate, urethane methacrylate, polyester acrylate, polyester methacrylate, and polyether. Examples thereof include acrylate and polyether methacrylate. One of these acrylic compounds and methacrylic compounds may be used alone, or two or more thereof may be used in combination.

  In addition, when an acrylic compound or a methacrylic compound is employed as the thiol-reactive compound, depending on the selected material, the cured film obtained by light irradiation becomes transparent. Can also be applied.

  Hereinafter, specific examples of the thiol-reactive compound will be given.

  It is preferable that content of the photothiol generator in the photosensitive resin composition of this invention shall be 1-1000 mass parts with respect to 100 mass parts of thiol reactive compounds. If the content of the photothiol generator is less than 1 part by mass, the thiol-reactive compound may not be allowed to react rapidly. On the other hand, if the content of the photothiol generator exceeds 1000 parts by mass, The presence of the generator may adversely affect the solubility of the thiol-reactive compound in the solvent, and the presence of an excessive amount of the photothiol generator leads to high costs. The content of the photothiol generator is preferably 5 to 300 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the thiol-reactive compound.

  When using the epoxy compound as the thiol-reactive compound, the photosensitive resin composition of the present invention has the above-mentioned No. 4-1. It is preferable to use an epoxy compound (polymerizable epoxy compound) exhibiting polymerization reactivity such as 4-12. Such a photosensitive resin composition is polymerized by the action of light or heat to give a polymer. Especially, it is preferable to set it as the photosensitive resin composition containing the photopolymerizable epoxy-type compound which starts a polymerization reaction with light.

  In order to form a pattern using the photosensitive resin composition according to the present invention, for example, the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is used as an appropriate solid such as a substrate. It is applied to the surface and dried to form a coating film. And after performing pattern exposure with respect to the formed coating film and generating thiol, it heat-processes on predetermined conditions, The polymerization reaction of the thiol reactive compound contained in the photosensitive resin composition is carried out. To encourage.

  If necessary, the photosensitive resin composition of the present invention preferably contains a photopolymerization initiator. By containing the polymerization initiator in the photosensitive resin composition of the present invention, the polymerization is smoothly started efficiently and the reaction efficiency is improved. Addition of a photopolymerization initiator is preferable when an acrylic compound, a methacrylic compound, or a maleimide compound that cures by a radical reaction is used as the thiol-reactive compound.

  The photopolymerization initiator that can be used is not particularly limited, and examples thereof include radical photopolymerization initiators such as bis (2,4,6-trimethylbenzoyl) phenyl phosphooxide, and JP2009-58582A. Can be used. Although the addition amount of a photoinitiator should just be suitably determined with the photothiol generator to be used, a thiol reactive compound, etc., it is the range of 0.1-10 mass% with respect to the whole photosensitive resin composition. Is preferable, and it is particularly preferable to be within the range of 0.5 to 5% by mass.

  Since the photosensitive resin composition of the present invention contains the photothiol generator of the present invention, the polymerization reaction proceeds even at room temperature, but it is preferable to perform a heat treatment so that the polymerization reaction proceeds efficiently. The heat treatment is preferable when an epoxy compound or an episulfide compound that cures by an ionic reaction is used as the thiol reactive compound.

  The heat treatment conditions may be appropriately determined depending on the exposure energy, the type of thiol generated from the photothiol generator used, and the type of thiol-reactive compound, but the heating temperature should be in the range of 50 ° C to 150 ° C. Is preferable, and it is particularly preferable to set the temperature within the range of 60 ° C to 130 ° C. The heating time is preferably 10 seconds to 60 minutes, particularly preferably 60 seconds to 30 minutes. The pattern can be obtained by immersing this in a solvent that causes a difference in solubility between the exposed part and the unexposed part and developing.

  In the photosensitive resin composition of the present invention, if necessary, a base generator that generates a base by an active energy ray such as light (photobase generator) or a base proliferator that generates a base proliferatively by the action of a base It is preferable to contain. The sensitivity of the resin composition can be further improved by adding a base generator or a base proliferating agent to the photosensitive resin composition of the present invention. In particular, when the light does not reach the deep part of the resin film (when the photosensitive layer is thick or contains a large amount of dye or pigment, etc.), the action of the photochemically generated base in the surface layer and the base by the base proliferating agent When the growth reaction is started, bases are generated thermochemically and in a chain manner, so that a base-catalyzed reaction in the deep part of the membrane can be expected. The addition of a base generator or a base proliferating agent is preferable when an epoxy compound or an episulfide compound that cures by an ionic reaction is used as a thiol reactive compound.

  The base generator that can be used is not particularly limited, and is a predetermined carboxylic acid and an amine such as a primary amine, secondary amine, or tertiary amine, a compound containing a pyridyl group, a hydrazine compound, an amide compound, water. Carboxylic acid compounds composed of bases such as quaternary ammonium oxide salts, mercapto compounds, sulfide compounds, and phosphine compounds can be used. For example, base generators described in JP 2011-236416 A are used. can do. Although the addition amount of a base generator should just be suitably determined with the photothiol generator to be used, a thiol reactive compound, etc., it is the range of 0.1-20 mass% with respect to the whole photosensitive resin composition. A range of 1 to 10% by mass is particularly preferable.

  Further, the base proliferating agent that can be used is not particularly limited, and examples thereof include JP-A No. 2000-330270 and JP-A No. 2002-128750. Arimitsu, M.M. Miyamoto and K.M. Ichimura, Angew. Chem. Int. Ed. , 39, 3425 (2000), and the like. The addition amount of the base proliferating agent may be appropriately determined depending on the photothiol generator or thiol-reactive compound to be used, but is preferably in the range of 1 to 40% by mass with respect to the entire photosensitive resin composition. A range of 5 to 20% by mass is particularly preferable.

  In the photosensitive resin composition of the present invention, a sensitizer can be added in order to expand the photosensitive wavelength region and increase the sensitivity. The sensitizer that can be used is not particularly limited. For example, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene. , Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro -4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2 tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5 , 7-dimethoxycarbonylcoumarin) or coronene. These sensitizers may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the addition amount of the sensitizer may be appropriately determined depending on the photothiol generator and thiol-reactive compound used, the required sensitivity, etc., but the photosensitive resin composition It is preferable that it is the range of 1-30 mass% with respect to the whole. If the sensitizer is less than 1% by mass, the sensitivity may not be sufficiently increased. On the other hand, if the sensitizer exceeds 30% by mass, the sensitivity may be excessive. The addition amount of the sensitizer is particularly preferably in the range of 5 to 20% by mass with respect to the entire photosensitive resin composition.

  When the photosensitive resin composition of the present invention is applied to a predetermined substrate, a solvent may be appropriately contained as necessary. By including a solvent in the photosensitive resin composition, the coating ability can be increased, and workability is improved. The solvent is not particularly limited. For example, aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, Saturated or unsaturated hydrocarbon compounds such as isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, Di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibuty Ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl Ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o- Ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

  In the photosensitive resin composition of the present invention, the content of the solvent is, for example, uniformly applied when a photosensitive resin composition is applied on a predetermined substrate to form a layer of the photosensitive resin composition. The selection may be made as appropriate.

  In addition, you may make it add an additive suitably to the photosensitive resin composition of this invention in the range which does not inhibit the objective and effect of this invention. Examples of additives that can be used include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, Examples thereof include a plasticizer, a plastic accelerator, an anti-sagging agent, a curing accelerator, and a filler. One of these may be used alone, or two or more may be used in combination.

The photosensitive resin composition of the present invention described above contains a photothiol generator and a thiol-reactive compound of the present invention, so that it has excellent curing speed and reaction efficiency, and curing is carried out quickly and cured. It becomes the photosensitive resin composition which is made sufficiently. In addition, since the contained photothiol generator generates thiol by a photocyclization reaction, carbon dioxide gas (CO ₂ ) is not generated as a decomposition product, and there is no unevenness, and product characteristics and product value are excellent. A cured film can be provided simply. The photosensitive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.

  In addition, the photosensitive resin composition of the present invention is a UV curable resin with extremely low volatile organic compounds (VOC), and is excellent in environmental adaptability. And since progress of reaction can be controlled by irradiation of light, even if it uses as a photocuring material, it becomes a photosensitive resin composition which has a long pot life and is excellent in storage stability.

  The molded body applied as a photo-curing material can be used as a member in a field where characteristics such as heat resistance, dimensional stability, and insulation are effective, for example, paint or printing ink, color filter, film for flexible display, semiconductor, etc. Widely used as equipment, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members or building materials, printed materials, color filters, films for flexible displays, A semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, a building member, or the like is provided. In addition, the formed pattern has heat resistance and insulation, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, reflective It can be advantageously used as a protective film, other optical member or electronic member.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this Example at all.

[Example 1]
Production of photothiol generator (1):
Using the operations (1) to (3) below, a photothiol generator represented by the formula (X-1) was produced.

(1) Production of intermediate (1):
In a 100 ml eggplant flask, 21.0 g (58 × 10 ⁻³ mol) of ethyl 2- (triphenylphosphoranylidene) propionate was placed in 200 ml of dehydrated benzene as a solvent and dissolved at room temperature. After dissolution, 10.0 g (82 × 10 ⁻³ mol) of salicylaldehyde was added and dissolved by stirring for 6 hours at room temperature. After completion of the reaction, the solvent was distilled off and diluted with chloroform. After washing three times with saturated saline, the organic layer was dried over anhydrous magnesium sulfate. After evaporation of the solvent, ethyl acetate and n-hexane were separated by column chromatography using a developing solvent of ethyl acetate / hexane = 1/4, dried under reduced pressure, and then an intermediate represented by the following formula (H-1) ( The white solid of 1) was obtained in a yield of 11.0 g and a yield of 94%.

(2) Production of intermediate (2):
11.0 g (53 × 10 ⁻³ mol) of the intermediate (1) obtained in (1) was placed in a 500 ml eggplant flask, and 150 ml of ethanol was added and dissolved. After dissolution, 60 ml of water and 14.0 g (250 × 10 ⁻³ mol) of potassium hydroxide (KOH) were added and heated at reflux for 5 hours. After completion of the reaction, the solvent was distilled off, diluted with chloroform, and washed with a 5 mass% hydrochloric acid aqueous solution until the pH reached 3-5. After distilling off the solvent and drying under reduced pressure, a white solid of the intermediate (2) represented by the following formula (H-2) was obtained in a yield of 10.0 g and a yield of 98%.

(3) Production of photothiol generator (1):
In a 100 ml eggplant flask, 0.48 g (2.7 × 10 ⁻³ mol) of the intermediate (2) obtained in (2) and 20 ml of dehydrated tetrahydrofuran (THF) were added and dissolved at room temperature. After dissolving, 0.60 g (3.17 × 10 ⁻³ mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) was added and stirred, and then a mixture of the following formula (T-1) was added. 0.60 g (2.9 × 10 ⁻³ mol) of 2-ethylhexyl thioglycolate, which is a functional thiol, was added and stirred at room temperature for 3 hours. After completion of the reaction, the solvent was distilled off, and chloroform and acetone were separated by column chromatography using a developing solvent of chloroform / acetone = 40/1. The yellow viscosity of the photothiol generator represented by the formula (X-1) A liquid was obtained with a yield of 0.69 g and a total yield of 64%.

[Example 2]
Production of photothiol generator (2):
In a 500 ml eggplant flask, 4.1 g (23 × 10 ⁻³ mol) of intermediate (2) obtained in Example 1 (2) and 100 ml of dehydrated tetrahydrofuran (THF) were added and dissolved at room temperature. After dissolution, 4.5 g (23 × 10 ⁻³ mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) was added and stirred, and then the polyfunctional thiol of the following formula (T-2) 1,4-bis (mercaptomethyl) benzene 1.9 g (11 × 10 ⁻³ mol) was added and stirred at room temperature for 4 hours. After completion of the reaction, the solvent was distilled off, and chloroform and acetone were separated by column chromatography using a developing solvent of chloroform / acetone = 40/1. The yellow viscosity of the photothiol generator represented by the formula (X-2) A liquid was obtained in a yield of 2.0 g and a total yield of 32%.

[Example 3]
Production of photothiol generator (3):
A 300 ml eggplant flask was charged with 2.0 g (11 × 10 ⁻³ mol) of the intermediate (2) obtained in Example 1 (2) and 50 ml of dehydrated tetrahydrofuran (THF) and dissolved at room temperature. After dissolution, 2.2 g (11 × 10 ⁻³ mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) was added and stirred, and then the polyfunctional thiol represented by the following formula (T-3) 3,6-dioxa-1,8-octanedithiol 1.0 g (5.5 × 10 ⁻³ mol) was added and stirred at room temperature for 4 hours. After completion of the reaction, the solvent was distilled off, and chloroform and acetone were separated by column chromatography using a developing solvent of chloroform / acetone = 13/1, and a white solid of the photothiol generator represented by the formula (X-3) Was obtained in a yield of 0.55 g and a total yield of 18%.

[Example 4]
Production of photothiol generator (4):
In a 500 ml eggplant flask, 4.0 g (22 × 10 ⁻³ mol) of intermediate (2) obtained in Example 1 (2) and 100 ml of dehydrated tetrahydrofuran (THF) were added and dissolved at room temperature. After dissolution, 4.5 g (23 × 10 ⁻³ mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) was added and stirred, and then the polyfunctional thiol of the following formula (T-4) 3.9 g (7.4 × 10 ⁻³ mol) of tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate was added and stirred at room temperature for 7 hours. After completion of the reaction, the solvent was distilled off, and chloroform and acetone were separated by column chromatography using a developing solvent of chloroform / acetone = 20/1, and a white solid of the photothiol generator represented by the formula (X-4) Was obtained in a yield of 2.5 g and a total yield of 31%.

[Example 5]
Production of photothiol generator (5):
In a 300 ml eggplant flask, 2.9 g (16 × 10 ⁻³ mol) of the intermediate (2) obtained in Example 1 (2) and 50 ml of dehydrated tetrahydrofuran (THF) were added and dissolved at room temperature. After dissolution, 2.8 g (17 × 10 ⁻³ mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDAC) and pentaerythritol tetrakis which is a polyfunctional thiol of the following formula (T-5) 1.9 g (3.8 × 10 ⁻³ mol) of (3-mercaptopropionate) was added and stirred at room temperature for 24 hours, and then the solvent was distilled off to remove chloroform and acetone from chloroform / acetone = 10/1. Was used for separation by column chromatography to obtain a white solid of the photothiol generator represented by the formula (X-5) in a yield of 0.56 g and a total yield of 12%.

[Test Example 1]
Confirmation of solubility in organic solvents:
The solubility of the photothiol generator obtained in Examples 2 to 5 in an organic solvent was confirmed. The results are shown in FIG. The solubility confirmed the amount of solvent melt | dissolved with respect to 0.01 g of photothiol generators. In FIG. 1, the result of the dissolution amount is expressed as “++” when the amount of solvent is less than 1 ml, “+” when it is 1 ml or more and less than 5 ml, “−” when it is 5 ml or more and less than 10 ml, and “−” when it is 10 ml or more. Indicated.

  FIG. 1 is a graph showing the solubility of the photothiol generator obtained in Examples 2 to 5 in an organic solvent. As shown in FIG. 1, all the obtained photothiol generators also showed good solubility in tetrahydrofuran (THF). In addition, the photothiol generator of Example 3 is soluble in cyclohexane and MEK, and the photothiol generators of Examples 2, 4 and 5 are organic solvents that exhibit good solubility. There were also some confirmed.

[Test Example 2]
Confirmation of photodegradation behavior (UV spectrum measurement):
About the photothiol generator obtained in Example 2 thru | or Example 5, methanol was used as a solvent and the photodegradation behavior was confirmed using the following measuring method.

(Measuring method)
A methanol solution of the photothiol generator of Example 2 to Example 5 at 2.0 × 10 ⁻⁵ mol / l was irradiated with light having wavelengths of 254 nm, 313 nm, and 365 nm, and an ultraviolet-visible spectrophotometer (MultiSpec-1500). (Manufactured by Shimadzu Corporation) was used to confirm the change with time of the UV spectrum.

  When the time-dependent change of the UV spectrum was confirmed, the photothiol generator obtained in Example 2 to Example 5 was changed in absorption with the exposure amount of light irradiation, and the photodegradation behavior was confirmed. In Example 2, peaks can be confirmed at 277 nm and 318 nm, in Example 3 at 272 nm and 317 nm, and in Examples 4 and 5, the peaks at 277 nm and 322 nm can be confirmed, but at 318 nm in Example 2, 317 nm in Example 3, The peak near 322 nm in 4 and Example 5 is a peak generated when a cyclization reaction occurs, and the photothiol generators of Examples 2 to 5 are subjected to a photocyclization reaction by exposure. It could be confirmed.

  2 to 4 are diagrams comparing the photodegradation behaviors of the photothiol generators of Examples 2 to 5 with wavelengths of 254 nm light, 313 nm light, and 365 nm light (FIG. 2 shows 254 nm light, FIG. 3 shows the result of 313 nm light, and FIG. 4 shows the result of 365 nm light.

Confirmation of photodegradation behavior (identification of photocyclized product):
The photocyclized product produced during the photodegradation behavior was identified. 0.10 g of the photothiol generator of Example 2 and 30 ml of tetrahydrofuran (THF) were placed in a 50 ml vial, irradiated with light having a wavelength of 365 nm, and the photocyclized product after exposure was isolated by column chromatography to obtain a white solid. The yield was 0.060 g and the yield was 92%. From the isolated compound ¹ H-NMR spectrum and the results of its assignment, it was confirmed that the photothiol generator of Example 2 caused a cyclization reaction by irradiation with light, and the cyclized product was 3-methylcoumarin.

[Test Example 3]
Confirmation of photodegradation behavior in polymer solids:
0.04 g of photothiol generator obtained in Example 2 (40 parts by mass with respect to 100 parts by mass of PTMG) with respect to 0.10 g of polytetrahydrofuran (polytetramethylene ether glycol) (PTMG) (8.2 × 10 ⁻⁵ mol) was added to obtain a photosensitive resin composition. Such a photosensitive resin composition is dissolved in 1.0 g of tetrahydrofuran (THF) to form a sample solution. This sample solution is spin-coated on a silicon wafer at 1000 rpm for 30 seconds, and prebaked at 80 ° C. for 30 seconds on a hot plate. By doing
A 1.0 μm film was prepared. This film was irradiated with 365 nm monochromatic light at an exposure amount of 0-20480 mJ / cm 2, and the reaction was monitored by FT-IR. The same operation was performed for the photothiol generators of Example 3 and Example 4, and the reaction was followed by FT-IR. The photothiol generator of Example 3 was 0.041 g (41 parts by mass with respect to 100 parts by mass of PTMG), and the photothiol generator of Example 4 was 0.082 g (82 parts by mass with respect to 100 parts by mass of PTMG). did.

  In addition, what was traced was a decrease in the peaks of the carbonyl group (C═O) and the hydroxy group (—OH) due to the decomposition of the photothiol generator of Examples 2 to 4, and the cyclized product expected to be produced. It is an increase in the peak of the carbonyl group (C = O) of (coumarin) and the mercapto group (-SH) of thiol.

As a result of tracking the IR spectrum, it was confirmed that Example 2 to Example 4 were decomposed by light having a wavelength of 365 nm, and the expected cyclized product and thiol were generated. In addition, the peak of the carbonyl group of the generated photocyclized product decreased as the exposure amount was increased. This is probably because the coumarin ring was dimerized by 365 nm light. The decomposition of all the photothiol generators of Examples 2 to 4 was completed at about 1000 mJ / cm ² .

[Example 6]
Production of photosensitive resin composition (1):
Example 2 with respect to 0.10 g of polyglycidyl methacrylate (PGMA, M _W = 11000 g / mol, M _W / M _n = 1.8) which is an epoxy compound represented by the formula (No. 4-12) 0.01 g (Example 6-1), 0.02 g (Example 6-2), 0.03 g (Example 6-3), 0.04 g (Example 6) 4) (Sequentially 10.0, 20.0, 30.0, 40.0 parts by mass with respect to 100 parts by mass of PGMA) (3.0, 6.0, 9.0, 12 with respect to the monomer unit of PGMA) (0.0 mol%), the photosensitive resin composition of the present invention was obtained.

[Example 7]
Production of photosensitive resin composition (2):
Example 3 with respect to 0.10 g of polyglycidyl methacrylate (PGMA, M _W = 11000 g / mol, M _W / M _n = 1.8) which is an epoxy compound represented by the formula (No. 4-12) 0.01 g (Example 7-1), 0.02 g (Example 7-2), 0.03 g (Example 7-3), 0.04 g (Example 7-) 4) (Sequentially 10.0, 20.0, 30.0, 40.0 parts by mass with respect to 100 parts by mass of PGMA) (3.0, 6.0, 9.0, 12 with respect to the monomer unit of PGMA) (0.0 mol%), the photosensitive resin composition of the present invention was obtained.

[Test Example 4]
Confirmation of photoinsolubilization behavior (1) (depending on heating time):
The photosensitive resin composition obtained in Example 6-3 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 30 seconds to produce a film having a thickness of 0.5 μm. This film was irradiated with 365 nm monochromatic light, post-baked at 100 ° C. for 30 minutes, developed with tetrahydrofuran (THF) for 30 seconds, and the thickness of the remaining film was measured. The illuminance was 10 mW / cm ² (the same applies to Test Examples 5 to 9 below). The same operation was performed with the post-baking time changed to 45 minutes and 60 minutes, and the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was created for each. The obtained sensitivity curve is shown in FIG.

[Test Example 5]
Confirmation of photoinsolubilization behavior (2) (depending on addition amount):
The photosensitive resin composition obtained in Example 6-1 (3.0 mol% with respect to the monomer unit of PGMA) was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 30 seconds to produce a film having a thickness of 0.5 μm. The film was irradiated with 365 nm monochromatic light, post-baked at 100 ° C. for 60 minutes, developed with tetrahydrofuran (THF) for 30 seconds, and the thickness of the remaining film was measured. Then, the same operations were performed as in Example 6-2 (similarly 6.0 mol%), Example 6-3 (similarly 9.0 mol%), and Example 6-4 (similarly 12.0 mol%). %)), And the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was prepared for each. The obtained sensitivity curve is shown in FIG.

[Test Example 6]
Confirmation of photoinsolubilization behavior (3) (depending on heating temperature):
The photosensitive resin composition obtained in Example 6-3 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds and prebaked on a hot plate at 80 ° C. for 30 seconds to obtain a thickness of about 0.5
A μm film was prepared. This film was irradiated with 365 nm monochromatic light, post-baked at 90 ° C. for 60 minutes, developed with tetrahydrofuran (THF) for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed while changing the post-baking temperature to 100 ° C. and 110 ° C., and the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was created for each. The obtained sensitivity curve is shown in FIG.

[Test Example 7]
Confirmation of photoinsolubilization behavior (4) (depending on heating time):
The photosensitive resin composition obtained in Example 7-3 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 30 seconds to produce a film having a thickness of 0.5 μm. This film was irradiated with 365 nm monochromatic light, post-baked at 100 ° C. for 30 minutes, developed with tetrahydrofuran (THF) for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed with the post-baking time changed to 45 minutes and 60 minutes, and the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was created for each. The obtained sensitivity curve is shown in FIG. As shown in FIG. 6 (A), it is confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) is improved as the exposure amount is increased and the heating time is increased in the range of 0 to 100 mJ / cm ^2. did it.

[Test Example 8]
Confirmation of photoinsolubilization behavior (5) (depending on addition amount):
The photosensitive resin composition (3.0 mol% based on the monomer unit of PGMA) obtained in Example 7-2 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 30 seconds to produce a film having a thickness of 0.5 μm. The film was irradiated with 365 nm monochromatic light, post-baked at 100 ° C. for 60 minutes, developed with tetrahydrofuran (THF) for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed on the photosensitive resin composition obtained in Example 7-3 (similarly 9.0 mol%) and Example 7-4 (similarly 12.0 mol%). The relationship (sensitivity curve) between the exposure amount and the remaining film rate was prepared for each. The obtained sensitivity curve is shown in FIG. As shown in FIG. 6 (B), in the range of 0 to 100 mJ / cm ² , the insolubilization efficiency of polyglycidyl methacrylate (PGMA) increases as the exposure amount is increased and the addition amount of the photothiol generator is increased. It was confirmed that it improved.

[Test Example 9]
Confirmation of photoinsolubilization behavior (6) (depending on heating temperature):
The photosensitive resin composition obtained in Example 7-3 was dissolved in 1.0 g of tetrahydrofuran (THF). This sample solution was spin-coated on a silicon wafer at 3000 rpm for 30 seconds, and prebaked on a hot plate at 80 ° C. for 30 seconds to produce a film having a thickness of about 0.5 μm. This film was irradiated with 365 nm monochromatic light, post-baked at 90 ° C. for 60 minutes, developed with tetrahydrofuran (THF) for 30 seconds, and the thickness of the remaining film was measured. The same operation was performed while changing the post-baking temperature to 100 ° C. and 110 ° C., and the relationship (sensitivity curve) between the exposure amount and the remaining film ratio was created for each. The obtained sensitivity curve is shown in FIG. As shown in FIG. 6 (C), it is confirmed that the insolubilization efficiency of polyglycidyl methacrylate (PGMA) increases as the exposure amount is increased and the heating temperature is increased in the range of 0 to 100 mJ / cm ^2. did it.

[Example 8]
Production of photosensitive resin composition (3):
0.096 g (Example 8-) of the photothiol generator obtained in Example 2 with respect to 0.10 g of sorbitol polyglycidyl ether (Denacol EX-622: manufactured by Nagase ChemteX Corp.) which is an epoxy compound. 1), 0.24 g (Example 8-2), 0.36 g (Example 8-3) (in order, 96, 240, 360 parts by mass with respect to 100 parts by mass of EX-622) (in EX-622 The photosensitive resin composition of the present invention was obtained by containing 150, 200, and 300 mol%).

[Example 9]
Production of photosensitive resin composition (4):
0.37 g (Example 9-) of the photothiol generator obtained in Example 4 with respect to 0.10 g of sorbitol polyglycidyl ether (Denacol EX-622: manufactured by Nagase ChemteX Corp.) which is an epoxy compound. 1), 0.50 g (Example 9-2), 0.74 g (Example 9-3) (in order, 370, 500, 740 parts by mass with respect to 100 parts by mass of EX-622) (monomer unit of PGMA) The photosensitive resin composition of the present invention was obtained by adding 150, 200, and 300 mol%).

[Test Example 10]
Curing test (addition amount dependency) (1):
The photosensitive resin composition obtained in Example 8-1 (150 mol% with respect to the monomer unit of the epoxy compound) was dissolved in 1.0 g of tetrahydrofuran (THF). A film was formed by bar coating on this sample solution calcium fluoride (CaF ₂ ), and prebaked by heating at 80 ° C. for 30 seconds to prepare a coating film having a thickness of 15 μm. The coating film was heated to 120 ° C. for 60 minutes at JIS K5600-5 with a monochromatic light of 365 nm applied to this coating film with an exposure amount of 0 (blank), 10, 100, 500, 1000 and 10000 mJ / cm ^2. The pencil hardness was measured according to 4 and compared and evaluated. And the same operation was implemented with respect to the photosensitive resin composition obtained in Example 8-2 (similarly 200 mol% thing) and Example 8-3 (similarly 300 mol% thing). The results are shown in FIG.

FIG. 7 is a diagram showing the relationship between the exposure amount and the pencil hardness in Test Example 10. In the range of 0 to 100 mJ / cm ² , it was confirmed that the curing progressed as the exposure amount was increased and the addition amount was increased.

[Test Example 11]
Curing test (addition amount dependency) (2):
The photosensitive resin composition obtained in Example 9-1 (150 mol% with respect to the monomer unit of the epoxy compound) was dissolved in 1.0 g of tetrahydrofuran (THF). A film was formed by bar coating on this sample solution calcium fluoride (CaF ₂ ) and prebaked by heating at 80 ° C. for 30 seconds to prepare a coating film having a thickness of 15 μm. The coating film was heated to 120 ° C. for 60 minutes at JIS K5600-5 with a monochromatic light of 365 nm applied to this coating film with an exposure amount of 0 (blank), 10, 100, 500, 1000 and 10000 mJ / cm ^2. The pencil hardness was measured according to 4 and compared and evaluated. And the same operation was implemented with respect to the photosensitive resin composition obtained in Example 9-2 (similarly 200 mol% thing) and Example 9-3 (similarly 300 mol% thing). The results are shown in FIG.

FIG. 8 is a diagram showing the relationship between the exposure amount and pencil hardness in Test Example 11. In the range of 0 to 100 mJ / cm ² , it was confirmed that the curing progressed as the exposure amount was increased and the addition amount was increased.

FIG. 9 shows the exposure amount and the remaining film ratio of the photosensitive resin compositions of Example 8 (Example 8-3) and Example 9 (Example 9-3) from the results of Test Example 10 and Test Example 11. It is the figure which compared the relationship (The heating temperature was 100 degreeC and the heating time was 60 minutes.). As shown in FIG. 9, as a whole, Example 8 (Example 8-3) had a higher residual film ratio than Example 9 (Example 9-3). In addition, when the exposure amount exceeded 100 mJ / cm ² , there was a tendency for the remaining film rate to decrease.

FIG. 10 is a view showing the relationship between the addition amount and the transmittance of the cured film obtained by light irradiation (the exposure amount was 100 mJ / cm ² ). As shown in FIG. 10, the obtained cured film showed a high transmittance at any addition amount, and it was confirmed that a cured film having excellent transparency was obtained.

  In addition, regarding the photosensitive resin compositions of Examples 6 to 9, the film obtained in [Test Example 1] to [Test Example 11] did not show unevenness due to the generation of carbon dioxide gas.

[Example 10]
Production of photosensitive resin composition (5):
0.15 g (375 parts by mass with respect to 100 parts by mass of PETA) of the photothiol generator obtained in Example 4 with respect to 0.04 g of pentaerythritol tetraacrylate (PETA) (PETA) which is an acrylic compound (PETA The photosensitive resin composition of this invention was obtained by making it contain 133.0 mol%). A small amount of tetrahydrofuran (THF) and a photothiol generator were mixed in advance and contained in PETA, and then THF was distilled off by drying under reduced pressure.

[Reference Example 1]
Production of photosensitive resin composition (6):
Tris-[(3-mercaptopropionyloxy)-represented by the following formula (T-6), which is a thiol compound (polyfunctional thiol), with respect to 0.04 g of pentaerythritol tetraacrylate (PETA), which is an acrylic compound. A photosensitive resin composition was obtained by containing 0.08 g of ethyl] -isocyanurate (TEMPIC) (200 parts by mass with respect to 100 parts by mass of PETA) (133.0 mol% with respect to PETA).

[Reference Example 2]
Production of photosensitive resin composition (7):
1,3,5-tris (3-mercapto) represented by the following formula (T-7), which is a polyfunctional thiol, with respect to 0.04 g of pentaerythritol triacrylate (PETA) (PETA), which is an acrylic compound (Butyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (NR-1) 0.085 g (213 parts by mass relative to 100 parts by mass of PETA) The photosensitive resin composition was obtained by containing 133.0 mol%).

[Test Example 12]
Check storage stability:
The photosensitive resin compositions of Example 10 and Reference Example 1 and Reference Example 2 were put in 1.0 ml microtubes, respectively, and the states of “immediately after production”, “1 hour after production” and “after 1 month after production” were observed. The storage stability was compared and evaluated. As for the evaluation criteria, the viscosity immediately after the production is in the state immediately after the tube is laid down, the one hour after the production, and the one month after the production is observed after observing the state after 5 minutes with the tube lying down. Was visually observed. An appearance photograph is shown in FIG.

  FIG. 11 is a view showing an appearance photograph of a microtube in Test Example 12 ((A) is immediately after manufacture, (B) is one hour after manufacture, and (C) is one month after manufacture)). As shown in FIG. 11, the viscosity of the photosensitive resin composition of Reference Example 1 increased 1 hour after production, and that of the photosensitive resin composition of Reference Example 2 increased after 1 month of production (the sample flowed even when the tube was placed sideways). I was able to confirm. On the other hand, the photosensitive resin composition of Example 10 did not increase in viscosity even after 1 month of production, and it was confirmed that the material was excellent in storage stability.

[Example 11]
Production of photosensitive resin composition (8):
0.38 g of the photothiol generator obtained in Example 4 (380 parts by mass with respect to 100 parts by mass of PETA) with respect to 0.1 g of pentaerythritol tetraacrylate (PETA) (PETA), which is an acrylic compound (PETA) The photosensitive resin composition of this invention was obtained by making it contain 133.0 mol%).

[Reference Example 3]
Production of photosensitive resin composition (9):
1,3,5-tris (3-mercapto) represented by the formula (T-7) which is a polyfunctional thiol with respect to 0.1 g of pentaerythritol triacrylate (PETA) (PETA) which is an acrylic compound 0.22 g of butyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (NR-1) (220 parts by mass relative to 100 parts by mass of PETA) The photosensitive resin composition was obtained by containing 133.0 mol%).

  In addition, the photosensitive resin composition of above-mentioned Example 11 and Reference Example 3 is a radical photopolymerization initiator bis (2,4,6-trimethylbenzoyl) phenyl phosphooxide (Irgacure 819: manufactured by Nagase Sangyo Co., Ltd.). ) Was also prepared by adding 1.0 part by mass of the photosensitive resin composition to 100 parts by mass.

[Test Example 13]
Curing test (heating temperature dependence):
The photosensitive resin composition obtained in Example 11 and Reference Example 3 was dissolved in 0.5 g of tetrahydrofuran (THF) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 80 ° C. for 1 minute and prebaked to prepare a coating film having a thickness of 15 μm. Monochromatic light of 254 nm (not added with a photopolymerization initiator) and 365 nm (added with a photopolymerization initiator) was applied to this coating film with an exposure amount of 0.01, 0.1, 0.5, 1, ^2, 5, 10 J / cm ² (without addition of a photopolymerization initiator) and 0.01, 0.1, 0.5, 1, 5, 10, 15, 20, 30 J / cm ² ( As a sample to which a photopolymerization initiator was added, the hardness of the coating film at room temperature was measured by pencil hardness in accordance with JIS K5600-5-4, and compared and evaluated. The results are shown in FIG. 12 (without addition of photopolymerization initiator) and FIG. 13 (with addition of photopolymerization initiator).

12 and 13 are diagrams showing the relationship between the exposure amount and the pencil hardness in Test Example 13, and it was confirmed that curing progressed as the exposure amount was increased and the heating temperature was increased. In addition, the photosensitive resin composition of Example 11 has a good sensitivity and a large exposure amount (when no photopolymerization initiator is added, it is 15 J / cm ² or more, and when 10 J / cm ² is added, the amount is large. The hardness was almost the same as in Reference Example 3 to which a functional thiol was added, and the hardnesses of 3H (not added with a photopolymerization initiator) and H (added) were obtained at the maximum.

[Test Example 14]
Preparation of UV cured film (confirmation of oxygen inhibition):
A photosensitive resin composition of Example 11 and Reference Example 3 (each added with a photopolymerization initiator) and PETA alone (similar to Example 11 and the like, 1 radical photopolymerization initiator was added to 100 parts by mass). The sample solution was dissolved in 0.05 g of tetrahydrofuran (THF) to prepare a sample solution, and this sample solution was bar coated on a glass substrate to form a film, heated at 80 ° C. for 1 minute, pre-baked, A coating film having a thickness of 15 μm was prepared. The coating film hardness at room temperature is measured in accordance with JIS K5600-5-4 by measuring 365 nm monochromatic light in an air or nitrogen atmosphere with an exposure amount of 15 J / cm ² , and the coating film hardness at room temperature, Comparison and evaluation. The results are shown in FIG.

  FIG. 14 is a diagram showing the relationship between the exposure amount and the pencil hardness in Test Example 14. PETA alone was hardly cured in air, and the influence of oxygen inhibition was confirmed. On the other hand, the photosensitive resin composition of Example 11 is similar to the photosensitive resin composition of Reference Example 3 containing a polyfunctional thiol that is considered to have a low influence of oxygen inhibition. There was no difference and no effect of oxygen inhibition was observed.

Moreover, reaction was traced by FT-IR about the coating film after light irradiation, and the change of the peak (810 cm < ^-1 >) area of C = C was confirmed. The change in the peak area of C = C was measured by measuring the peak area before light irradiation, calculating the peak area after light irradiation when the pre-light irradiation was 1, and confirming the rate of change. The results are shown in FIG.

FIG. 15 is a graph showing the relationship between the exposure amount and the change rate of the C = C peak (810 cm ⁻¹ ) area ((A) is Example 11, (B) is Reference Example 3, and (C) is PETA alone. ). As shown in FIG. 15 (A), the photosensitive resin composition of Example 11 containing the photothiol generator of the present invention has the photosensitivity of Reference Example 3 containing a polyfunctional thiol considered to have a low influence of oxygen inhibition. As in the case of the conductive resin composition (FIG. 15B), the rate of change between the air and the nitrogen atmosphere is not much different, and the C = C double bond after irradiation is 0.3 to 0.4 before irradiation. It was confirmed that the reaction was carried out efficiently. On the other hand, as shown in FIG. 15C, for PETA alone, the C = C double bond after irradiation is about 0.8 before irradiation in the air, and that in a nitrogen atmosphere. Is larger than about 0.4. This is presumably because the polymerization is inhibited (oxygen inhibition) due to the presence of oxygen in the air and the reaction does not proceed efficiently.

  In addition, about the photosensitive resin composition of Example 10 and Example 11, the unevenness | corrugation by carbon dioxide gas generation | occurrence | production was not seen about the film | membrane obtained by [Test Example 12]-[Test Example 14].

The present invention can be advantageously used as a photosensitive resin material that provides a highly sensitive photocuring material, resist material (pattern forming material), and the like.

Claims (5)

The photothiol generator characterized by being represented by following formula (X).
(In Formula (X), R ₁ is an organic group, which may be a linear structure, a branched structure, or a cyclic structure, and may contain a hetero atom. Further, R ₁ includes a silyl group, an acryl group, and a methacryl group. R ₂ may be a halogen, a hydroxyl group, a sulfide group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, or a sulfonate group. Group, phosphino group, phosphinyl group, phosphono group, phosphonato group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group, alkoxy group, amino group, amide group, aryl group, allyl group, or organic group R ₃ is a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, Rufo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group, alkoxy group, amino group, amide group, aryl group, allyl group Furthermore, R ₂ and R ₃ may contain a polymerizable group such as a silyl group, an acryl group, or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them. ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, Phosphono group, phosphonato group, carboxyl group, carbonyl group, ester group, formyl group, acyl group, cyano group Alkoxy group, an amino group, an amide group, an aryl group, an allyl group, an ammonio group or an organic group, and may be be the same or different. Furthermore, the R _{4, R 5,} R ₆ and R ₇ , A silyl group, an acryl group, a methacryl group, or a monomer or a polymer obtained by polymerizing them, and R ₄ , R ₅ , R ₆ and R ₇ are those represented by 2 Two or more may be bonded to form a cyclic structure, and may include a heteroatom bond.) A photothiol generator represented by the following formula (X-a):
(In the formula (Xa), l and m are integers of 0 to 8, n is an integer of 1 to 6, Y is a tetravalent carbon, aromatic ring, triazine ring, or organic group, and the organic group is straight It may be a chain structure, a branched structure, or a cyclic structure, and may contain a heteroatom, and Y may contain a polymerizable group such as a silyl group, an acryl group, or a methacryl group, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same as those in the above formula (X), and R ₈ is an ester group or amide which is a functional group. And represents oxygen, sulfur which is a group, amino group, carbonyl group, alkyl group, or hetero atom.) The R ₂ is an alkyl group having 1 to 12 carbon atoms, and the R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms. Photothiol generator.   A photosensitive resin composition comprising the photothiol generator according to any one of claims 1 to 3 and a thiol-reactive compound.   The photosensitive resin according to claim 4, wherein the thiol-reactive compound is at least one selected from the group consisting of an epoxy compound, an episulfide compound, an acrylic compound, a methacrylic compound, and a maleimide compound. Composition.