WO2010119493A1 - Photosensitive compound and photocuring resin composition comprising same - Google Patents

Abstract

Disclosed are a photosensitive compound, a cured film of which has high flexibility, excellent chemical resistance, excellent heat resistance and good quick-curability and which can be recycled from waste plastics, and a photocuring resin composition comprising said photosensitive compound. Specifically disclosed is a photosensitive compound obtained by depolymerizing a polyester using a polyol having a plurality of hydroxyl groups per molecule, and then reacting the depolymerized product with a compound having a functional group, which is capable of reacting with a hydroxyl group, and an ethylenically unsaturated group. In a preferred case, said polyol having a plurality of hydroxyl groups per molecule is characterized by containing trimethylolpropane as a component thereof.

Description

Photosensitive compound and photocurable resin composition containing the same

The present invention relates to a photosensitive compound that gives a cured product excellent in heat resistance, adhesion and the like, and a photocurable resin composition containing the same.

UV curing resins are used in large quantities in adhesives, printing inks, various coating agents, etc., from the viewpoint of rapid curing and energy saving. Further, as a photoresist mixed with a carboxyl group-containing resin to impart alkali developability, it is used as a circuit forming resist, a plating resist, a solder resist, etc. in printed circuit board applications. In addition, it is used as a color filter, black matrix, and overcoat agent in flat panel display applications.

These UV curable resins are generally polyester acrylate, epoxy acrylate, urethane acrylate and the like, and most of them are liquid compounds from the viewpoint of fast curing. However, in the case of liquid compounds, there are many cases where there are problems in heat resistance characteristics such as reflow resistance and solder heat resistance, which are characteristics required for many electronic materials. In addition to heat resistance, adhesion and flexibility are properties that are strongly required for adhesion, printing ink, various coating agents, and the like.

On the other hand, in recent years, PET bottles made from polyester have been rapidly used in light weight, excellent in transparency, gas barrier properties, and high in strength, and the disposal method thereof has become a social problem. For this reason, PET bottles are generally collected separately and recycled. However, in the recycling process, there is a problem that the molecular weight of PET decreases due to hydrolysis of ester bonds, and the melt viscosity and mechanical strength of PET decrease. Such a decrease in quality is a factor in inhibiting the recycling of PET bottles. Therefore, at present, recycled PET resin is mainly used only in the field of fibers and industrial materials. However, as the amount of discarded PET bottles increases, a new effective method of using recycled PET resin is sought. ing.
Examples of such new methods include the production of alkyd resins for paints using a depolymerization reaction with glycols (see Patent Document 1), the production of polyester resins for paints using recycled polyester (see Patent Document 2), and further regeneration. Utilization of polyester as a raw material for a photocurable urethane resin (see Patent Document 3) has been studied.

Japanese Patent No. 3310661 (Claims) Japanese Patent No. 3443409 (Claims) JP 2004-307779 A (Claims, Examples)

The present invention has been made in view of the prior art as described above, and its purpose is excellent in flexibility, chemical resistance, heat resistance, and fast curability of a cured coating film, and can be recycled from waste plastic. It is providing the photocurable resin composition containing such a photosensitive compound and such a photosensitive compound.

In order to achieve the above object, according to the present invention, the photosensitive compound is obtained by depolymerizing a polyester with a polyol having a plurality of hydroxyl groups in one molecule, and further with a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. It is obtained by reacting a compound having a group.
In this case, preferably, the polyester is a regenerated polyester, and the polyol component having a plurality of hydroxyl groups in one molecule contains at least trimethylolpropane, and further a functional group capable of reacting with the hydroxyl groups. The compound having an ethylenically unsaturated group is preferably acrylic acid or methacrylic acid or a derivative thereof. The obtained photosensitive compound is a solid, semi-solid or fluid liquid.

In a preferred embodiment, a photosensitive compound represented by the following general formula (1) is provided.

(In the formula, R ¹ represents an (m + 1 + k) -valent polyhydric alcohol derivative, and R ² and R ⁵ each independently represents one of CH ₂ , C ₂ H ₄ , C ₃ H ₆ , and C ₄ H _8. , R ³ and R ⁴ each independently represents a substituted or unsubstituted aromatic ring, R ⁶ represents a hydrogen atom or a methyl group, j, k and n are each an integer of 1 or more, and l and m are Each is an integer of 0 or 1 or more.)

Furthermore, according to the present invention, there is provided a photocurable resin composition comprising the photosensitive compound represented by the general formula (1) and a photopolymerization initiator.

The photosensitive compound of the present invention and the photocurable resin composition containing the same are depolymerized from the photosensitive compound having the structure represented by the general formula (1), particularly a polyol having a plurality of hydroxyl groups in one molecule. Because it uses a photosensitive compound obtained by reacting a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group, it has high sensitivity, heat resistance, chemical resistance, moisture resistance, flexibility, etc. Can form a cured film excellent in In addition, when the photosensitive compound is 100% non-volatile and semi-solid, it can be suitably used for UV-curing adhesives, sealants, etc. In addition, various solvents and reactive diluents can be added to various coating agents and paints. Can be used. Further, when the polyester is a polyester recovered from a waste product, a high-concentration recycled resin can be used, so that it can be applied to a product that can contribute to CO ₂ reduction from the viewpoint of environmental protection.

2 is an infrared absorption spectrum of the photosensitive compound obtained in Synthesis Example 1.

As described above, the photocurable resin composition of the present invention is characterized in that a photosensitive compound or oligomer having a structure represented by the general formula (1) is used as the photosensitive resin.
According to the study by the present inventors, a photosensitive compound or oligomer having the structure represented by the general formula (1), in particular, a polyester was depolymerized with a polyol having a plurality of hydroxyl groups in one molecule and produced. The photosensitive compound or oligomer obtained by reacting a hydroxyl group with a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group is highly sensitive in heat resistance, chemical resistance, moisture resistance, flexibility, etc. I found it excellent. This is presumably because the resulting photosensitive compound or oligomer is semi-solid and has an aromatic ring, so that the moisture resistance, heat resistance and chemical resistance are improved. Here, it was found that when trimethylolpropane was used as the polyol having a plurality of hydroxyl groups in one molecule, the characteristics were most exhibited. That is, when trimethylolpropane is used as the polyol to be depolymerized, the synthesized photosensitive compound or oligomer becomes trifunctional and sensitivity can be increased. Further, only the oligomer precursor (alcohol) depolymerized with trimethylolpropane reduces the crystallinity of the polyester and has no cloudiness. For example, when an equimolar amount of trimethylolpropane is used as the PET repeating unit, the molecular weight Mn 700˜ A non-turbid resinous (amorphous) material of 100% non-volatile content is obtained. This precursor has no crystal precipitates even after 3 months, is transparent, has extremely high solubility in a solvent, and has a functional group capable of reacting with a hydroxyl group described later and an ethylenically unsaturated group. It was revealed that the compound can be easily synthesized under mild conditions. Here, when a trifunctional alcohol such as propylene glycol is used without using trimethylolpropane, it does not become turbid immediately after depolymerization, but crystals are formed and left turbid after standing for several days. The crystals did not dissolve in the solvent and had to be dissolved at a temperature close to 200 ° C. for further dissolution. Such a phenomenon was surprising and unexpected.

Polyesters used for the synthesis of the photosensitive compound or oligomer having the structure represented by the general formula (1) can be used as long as they are conventionally known polyesters. Among them, polyethylene terephthalate (PET) polytrimethylene terephthalate ( PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and PET bottles, PET films, and other waste products from the production of PET products, recovered from waste Recycled PET that has been washed and washed can be used. Preferred is recycled PET, but these can be obtained from the market as washed and pelletized.

The polyol having a plurality of hydroxyl groups in one molecule may be any bifunctional or higher polyol, and is not limited to a specific one. Bifunctional polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, spiroglycol, dioxane glycol, adamantane Diol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,1,4-cyclohexanedimethanol, 2-methylpropanediol, 1,3,3-methylpentanediol, Ethylene oxide of bifunctional phenols such as 1,5-hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A Modified compounds, propylene oxide modified compounds of bifunctional phenols such as bisphenol A, ethylene oxide, propylene oxide copolymerized modified compounds of bifunctional phenols such as bisphenol A, polyether polyols copolymerized with ethylene oxide and propylene oxide, carbonate diol Polyester diols, adamantane diols, polyether diols, polyester diols, hydroxyl-terminated polyalkanediene diols, such as 1,4-polyisoprenediol, 1,4- and 1,2-polybutadiene diols and their hydrogenated products Elastomers). As a commercially available product, for example, as an example of a commercially available product of the above hydroxyl group-terminated polyalkanedienediol, Epaul (manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene diol, molecular weight 1,860, average polymerization degree 26), PIP ( Idemitsu Petrochemical Co., Ltd., polyisoprene diol, molecular weight 2,200, average polymerization degree 34), polytail HA (Mitsubishi Chemical Corporation, hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39), R-45HT (Idemitsu) And petrochemicals, polybutanediol, molecular weight 2,270, average polymerization degree 42), and the like. Examples of the tri- or higher functional polyol include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and more. Ethylene oxide or propylene oxide modified products are also included. Examples of the polyol having an aromatic ring include ethylene oxide or propylene oxide modified products of trifunctional or higher functional phenol compounds, and examples having a heterocyclic ring include Sake manufactured by Shikoku Kasei Kogyo Co., Ltd. These polyols can be used alone or in combination of two or more. Among these, trifunctional polyols typified by carbonate diols and trifunctional polyols typified by trimethylolpropane can be used to obtain amorphous semi-solid fluid materials that do not become turbid when converted into depolymerized products. Furthermore, the solubility in a solvent is high, which is preferable. Furthermore, the depolymerized product obtained when depolymerized with trimethylolpropane has a high carbon ratio derived from polyester, and the recycled resin utilization rate increases when recycled polyester is used. Therefore, among the above polyols, it is preferable to use trimethylolpropane and / or a derivative thereof or a polyol containing them, and the polyol further contains 20 mol% or more of trimethylolpropane and / or a derivative thereof. Is particularly preferred.

For the reaction of depolymerizing the polyester with a polyol having a plurality of hydroxyl groups in one molecule, a conventionally known depolymerization method can be adopted. Preferably, the polyester is heated and dissolved without using a solvent. In the state, a polyol in a liquid state (in the case of solid, dissolved by heating to make a liquid) is added, and the reaction is preferably performed at about 200 to 300 ° C. in the presence of a catalyst.

In order to promote the depolymerization, a depolymerization catalyst can be used. Examples of the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate, and calcium acetate. , Lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like. The amount of these depolymerization catalysts used is usually in the range of 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of polyester and polyol. Although not a depolymerization catalyst, water is a compound that promotes depolymerization. This is present as an impurity in, for example, recycled PET, and causes a decrease in molecular weight when PET is recycled. Therefore, it is usually necessary to remove it by a very energy-consuming process such as drying. is there. However, in the production of the photosensitive compound of the present invention, it is not necessary. Rather, it is better to use regenerated PET pellets that are once melted and kneaded in a pellet making machine such as an extrusion molding machine after adding water. Is low, the reaction temperature at the time of depolymerization can be lowered, and the viscosity at the time of melting is low.

The blending ratio of the polyester and the polyol is such that the ratio of the number of moles of repeating units of the polyester (hereinafter abbreviated as a) and the number of moles of the polyol (hereinafter abbreviated as b) is (a) / (b) = 0. Desirably, it is within the range of 5 to 3, preferably 0.8 to 2. When the ratio is less than 0.5, the polyol is excessively contained, the ratio of the aromatic ring derived from the polyester is decreased, and the effect of improving heat resistance and chemical resistance is decreased, which is not preferable. On the other hand, when the ratio is larger than 3, the molecular weight of the depolymerized product is large, and a polyester-derived crystallized product exists, which has a functional group capable of reacting with a subsequent hydroxyl group and an ethylenically unsaturated group. It is not preferable because it is insoluble in the solvent used when the compound is reacted.

The photosensitive polymer or oligomer of the present invention can be obtained by reacting the depolymerized product obtained as described above with a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. This reaction is usually carried out at 80 to 120 ° C. for 2 to 10 hours in the presence or absence of an organic solvent, which will be described later, with the addition of an acid catalyst and a polymerization inhibitor. The synthesis can be carried out at normal pressure or under pressure, and the reaction temperature can be lowered under pressure.

Examples of the compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, (meth) acrylic acid caprolactone adduct, and half ester compounds of saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule, etc. Is mentioned. Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and phenylglycidyl (meth) acrylate. Examples of the dibasic acid anhydride for producing the half ester compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydro And phthalic anhydride. Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.
In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Here, the blending ratio of the depolymerized product of polyester and polyol (hereinafter abbreviated as ab), a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group (hereinafter abbreviated as c) is: These reaction ratios are within the range [molar equivalent of hydroxyl group of (ab)] / [molar equivalent of carboxyl group of (c)] = 0.8 to 2.0, preferably 0.9 to 1.5. It is desirable to be. The photosensitive compound or oligomer obtained at a ratio of 1 or more contains unreacted hydroxyl groups derived from the depolymerized product (ab), but there is no problem in characteristics even if some hydroxyl groups are present.

The photocurable resin composition of this invention is obtained by mix | blending the above photosensitive compounds or oligomer with a photoinitiator.
As the photopolymerization initiator, one or more light selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. A polymerization initiator can be used.
Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms) Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1), and substituted with an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group. Alkyl group having 8 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms, or a dialkyl group) Substituted with an amino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl). n is represented by an integer of 0 or 1.
In particular, in the chemical formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. Is preferred. )

The blending amount of such an oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When it is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.
Specific examples of α-aminoacetophenone photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

Specific examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.

In addition, as a photopolymerization initiator, a photoinitiator assistant, and a sensitizer that can be suitably used for the photocurable resin composition of the present embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, Examples include benzophenone compounds, tertiary amine compounds, and xanthone compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.
Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.
Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.
Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), Dialkylaminobenzophenones such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylamino Ethyl benzoate (n-butoxy) ethyl (Quantacue BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, a thioxanthone compound is preferably included from the viewpoint of deep curability. Of these, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferably included.

The compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, so it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition, and reflects the color of the colored pigment itself. It becomes possible to provide a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.
The blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease. More preferably, it is 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.
In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiators, photoinitiator assistants, and sensitizers may function as ultraviolet absorbers. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to enhance the photoreactivity of the surface, and changes the resist line shape and opening to vertical, tapered, and inversely tapered, and processing accuracy of line width and opening diameter Can be improved.

In the photocurable resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5 Lerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4- Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.

The aforementioned chain transfer agents can be used alone or as a mixture of two or more.
The total amount of such chain transfer agents is preferably in the range of 10 parts by mass or less with respect to 100 parts by mass of the photosensitive compound or oligomer. When it exceeds 10 parts by mass, the deep curability tends to decrease due to light absorption.

The photocurable resin composition of the present invention can be blended with a photoreactive diluent as required. Representative examples of the photoreactive diluent include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol Mono- or di (meth) acrylates of glycols such as; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate, etc. Aminoalkyl (meth) acrylates of the following: polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate or the like Poly (meth) acrylates of ethylene oxide or propylene oxide adducts; ethylene oxides of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A or (meth) acrylates of propylene oxide adducts Glyceryl diglycidyl ether, trimethylolpropane triglycidyl ether, (meth) acrylates of glycidyl ether such as triglycidyl isocyanurate; and melamine (meth) acrylate, and further, hydroxyl group-containing (meth) acrylate and polyvalent A reaction product with an anhydride of a carboxylic acid compound can be mentioned, but a reactive diluent that does not contain a hydroxyl group is preferred because a composition with better storage stability can be obtained. The photoreactive diluent can be used alone or in admixture of two or more, and not only acts as a diluent, but also contributes to acceleration of photocurability of the composition and improvement of developability. The blending ratio of the photoreactive diluent can be blended in an appropriate amount depending on the coating method of the composition, but generally 0 to 200 parts by weight with respect to 100 parts by weight of the photosensitive compound or oligomer, 20 to 100 parts by mass is preferable.

In the photocurable resin composition of the present invention, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75% by mass or less, more preferably 0.1 to 60% by mass of the total amount of the composition. If the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition is increased, and the coating and moldability are lowered, and the cured product becomes brittle.

In the photocurable resin composition of the present invention, an organic solvent can be used for the preparation of the synthesis reaction and the composition, or for adjusting the viscosity for application to a substrate or a carrier film.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

The photo-curable resin composition of the present invention may be a known conventional polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, fine silica, organic bentonite, and montmorillonite, if necessary. Conventional thickeners, pigments, dyes, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, Known and commonly used additives such as a rusting agent can be blended.

The photopolymerization composition of the present invention contains a binder resin (thermoplastic resin) or a thermosetting resin for the purpose of improving flexibility, touch-drying property, heat resistance, electrical insulation and other properties. Can do. As the binder resin, polymers such as cellulose, polyester, and phenoxy resin are preferable. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., a polyester-based polymer byron series manufactured by Toyobo Co., Ltd., and a phenoxy resin-based polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred.

As the thermosetting resin used in the present invention, amino resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives and the like are used. A thermosetting resin can be used. Particularly preferred is a thermosetting resin having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule, that is, a polyfunctional having at least a plurality of epoxy groups in the molecule. An epoxy resin, a polyfunctional oxetane compound having at least a plurality of oxetanyl groups in the molecule, and an episulfide resin having a plurality of thioether groups in the molecule.

When using a thermosetting resin having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT (registered trademark) 3503N, U-CAT3502T (both dimethyl) Trade names of amine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in sequence, resulting in functional deterioration of the polymer material. Therefore, the photocurable resin composition of the present invention is oxidized. Antioxidants such as radical scavengers that invalidate the generated radicals to prevent them and / or peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals Can be added.

Specific examples of the antioxidant that acts as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p- Cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6, - tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN Product name).

Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one, for example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

The photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method. A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C., followed by volatile drying (temporary drying). Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and making it dry and winding up as a film together on a base material.

As described above, the photocurable resin composition of the present invention is applied, and (after volatilized and dried if necessary) the obtained coating film is irradiated with active energy rays and cured.
As an exposure machine used for the active energy ray irradiation, a UV curing conveyor apparatus equipped with a high-pressure mercury lamp, a metal halide lamp, or a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a CAD data from a computer), Use an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp. Can do. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure amount varies depending on the film thickness and the like, but can generally be in the range of 5 to 2000 mJ / cm ² , preferably 5 to 1000 mJ / cm ² .

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Synthesis example 1
Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 134 parts of trimethylolpropane previously heated to 130 ° C. and dissolved were added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was transparent yellow and soft tones at room temperature. To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 10 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is referred to as abc-1 resin. The infrared absorption spectrum of the obtained abc-1 resin is shown in FIG.

Synthesis example 2
Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 93.8 parts of trimethylolpropane previously heated and dissolved at 130 ° C. were added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was transparent yellow and soft tones at room temperature. To 124 parts of the resulting reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 64.7 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 10 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is referred to as abc-2 resin.

Synthesis example 3
A 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen inlet tube, and cooling tube was charged with 39 parts of recycled PET flakes having an IV value of 0.6 to 0.7, and the atmosphere in the flask was changed to 300 ° C. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.40 part of dibutyltin oxide was added. Next, 161 parts of DURANOL T5650J (manufactured by Asahi Kasei Chemicals Corporation) preheated at 130 ° C. was added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was transparent yellow and soft tones at room temperature. To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 14.5 parts of acrylic acid, 0.43 part of paratoluenesulfonic acid, and 0.06 part of paramethoxyphenol were added, reacted at 110 ° C. for 10 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is referred to as abc-3 resin.

Synthesis example 4
A 500 milliliter four-necked round bottom separable lasco equipped with a stirrer, nitrogen introduction tube, and cooling tube was charged with 250 parts of recycled PET flakes having an IV value of 0.6 to 0.7, and the atmosphere in the flask was changed to a nitrogen atmosphere. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 104 parts of DURANOL T5650J (manufactured by Asahi Kasei Chemicals Corporation) and 157 parts of trimethylolpropane previously heated at 130 ° C. were added little by little while taking care not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was a yellow transparent liquid at room temperature. To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 63 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added, reacted at 110 ° C. for 10 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is referred to as abc-4 resin.

Synthesis example 5
Charged 192 parts of recycled PET flakes with an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen inlet tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Subsequently, 134 parts of trimethylolpropane previously heated to 130 ° C. and dissolved were added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the salt bath was replaced with an oil bath that was previously heated to 240 ° C., and the temperature in the flask was kept at 220 ° C. ± 10 ° C. for 5 hours. The reaction product was transparent yellow and soft tones at room temperature. To 170 parts of the obtained reaction product, 100 parts of toluene and 101 parts of methyl isobutyl ketone were introduced and mixed. Next, 132 parts of methacrylic acid, 5.28 parts of paratoluenesulfonic acid, and 0.13 part of paramethoxyphenol were added, reacted at 110 ° C. for 4 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred. Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. This is referred to as abc-5 resin.

Table 1 shows the recycled resin usage rate, appearance, nonvolatile content, shape, hydroxyl value, acrylated rate, recycled resin usage rate, molecular weight, and solvent solubility of the reactants obtained in Synthesis Examples 1 to 4. The solvent solubility evaluation method is as follows.
○: Dissolved ×: Not dissolved

Examples 1 to 4
Each of the photosensitive resins obtained in Synthesis Examples 1 to 4 was mixed with a photopolymerization initiator at a ratio shown in Table 2 and stirred to prepare a photocurable resin composition.

(1) Rubbing test The photocurable resin composition of each said Example was apply | coated to the glass plate with the film thickness of 20 micrometers using the applicator. The photocurable resin composition applied to the glass substrate was exposed at an exposure amount of 1 J / cm ² using a conveyor type exposure apparatus equipped with a high-pressure mercury lamp to obtain a cured coating film. The cured coating film thus obtained was rubbed 50 times with a waste cloth containing acetone, and it was judged that the one having no surface dissolution was sufficiently cured, and a slight dissolution was observed on the surface. Was evaluated as x. The evaluation results are shown in Table 3.

(2) Pencil hardness test A B-9H pencil sharpened so that the tip of the pencil core is flattened on the cured coating film obtained in the same manner as in (1) above was 45 ° C against the coating film. A pressure of 1 kg was applied with a load of 1 kg. The coated film was scratched by about 1 cm in a state where this load was applied, and the hardness of the pencil on which the coated film was not peeled was recorded. The results are shown in Table 3.

(3) Heat resistance test The cured coating film obtained in the same manner as in the above (1) was put into a 200 ° C hot-air circulating drying furnace and heated for 3 minutes. The sample was taken out after heating, and a heat resistance test was performed by visually observing the evidence of melting. The case where no melting or change was observed was evaluated as ◯, and the case where partial melting or change was confirmed was evaluated as X. The evaluation results are shown in Table 3.

Example 5
The abc-1 resin in Table 2 was replaced with the abc-5 resin obtained in Synthesis Example 5, and a photocurable resin was prepared. A rubbing test and a heat resistance test were conducted in the same manner as described above. No change was confirmed. Further, a pencil hardness test was conducted in the same manner as described above, and it was 4H.

As described above in detail, the photosensitive compound of the present invention is excellent in toughness, chemical resistance, heat resistance, and fast curability of the cured coating film, and further, because it is recycled from waste plastic, it has a burden on the environment. It can be reduced and is useful as a photosensitive compound in various fields.

Claims (4)

1. It is obtained by depolymerizing a polyester with a polyol having a plurality of hydroxyl groups in one molecule and reacting a compound having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. Photosensitive compound.
2. The photosensitive compound of Claim 1 shown by following General formula (1).
   

   

   
   (In the formula, R ¹ represents an (m + 1 + k) -valent polyhydric alcohol derivative, and R ² and R ⁵ each independently represents one of CH ₂ , C ₂ H ₄ , C ₃ H ₆ , and C ₄ H _8. , R ³ and R ⁴ each independently represents a substituted or unsubstituted aromatic ring, R ⁶ represents a hydrogen atom or a methyl group, j, k and n are each an integer of 1 or more, and l and m are Each is an integer of 0 or 1 or more.)
3. 3. The photosensitive compound according to claim 1, wherein trimethylolpropane is contained in a polyol component having a plurality of hydroxyl groups in one molecule.
4. A photocurable resin composition comprising the photosensitive compound according to claim 1 or 2 and a photopolymerization initiator.

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