JP2006290999A - Base agent for photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base agent for a photosensitive resin composition which adds suitable hardness, elasticity and excellent durability and chemical resistance and has excellent curability and developability, and also to provide a photosensitive resin composition using the same. <P>SOLUTION: A resin which has an ethylenic unsaturated group with a group represented by formula (I), -OCOCH(R<SP>1</SP>)CH<SB>2</SB>SR<SP>2</SP>(where R<SP>1</SP>is a hydrogen atom or a methyl group and R<SP>2</SP>is a 1-12C hydrocarbon group with 1 or 2 carboxy groups) is provided. The base agent for the photosensitive resin composition contains the above resin having an ethylenic unsaturated group. Also, the photosensitive resin composition contains the base agent containing the resin having an ethylenic unsaturated group with the group represented by formula (I), a polyfunctional monomer and a photo polymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a base for a photosensitive resin composition. More specifically, the present invention relates to a base for a photosensitive resin composition that can be suitably used as a resin component of the photosensitive resin composition, and a photosensitive resin composition using the same. The photosensitive resin composition of the present invention can be suitably used for, for example, inks, adhesives, insulating materials, electronic materials and the like.

  Generally, the resin component used as the base of the photosensitive resin composition has an ethylenically unsaturated group for photocurability and a carboxyl group for imparting developability. A negative photosensitive resin composition using a resin component having a carboxyl group is used for forming a desired pattern through exposure and development processes.

  In recent years, photosensitive resins have been required to improve various properties. For example, in order to improve hardness, elasticity, water resistance and chemical resistance, resins having a high glass transition temperature and a high crosslinking density are required. (See, for example, Patent Document 1).

However, when the glass transition temperature and the crosslink density are increased, the developability tends to decrease, so that it is necessary to increase the number of carboxyl groups, but on the other hand, there is a disadvantage that water resistance and chemical resistance are decreased.
Japanese Patent Laid-Open No. 10-31308

  The present invention has been made in view of the prior art, and provides a base for a photosensitive resin composition that imparts suitable hardness and elasticity, excellent durability and chemical resistance, and is excellent in curability and developability. Another object of the present invention is to provide a photosensitive resin composition using the same.

The present invention
(1) Formula (I):
—OCOCH (R ¹ ) CH ₂ SR ² (I)
(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 12 carbon atoms having one or two carboxyl groups)
A base for a photosensitive resin composition comprising an ethylenically unsaturated group-containing resin having a group represented by:
(2) comprising a base for a photosensitive resin composition containing an ethylenically unsaturated group-containing resin having a group represented by formula (I), a polyfunctional monomer, and a photopolymerization initiator, Photosensitive resin composition, and (3) Formula (I):
—OCOCH (R ¹ ) CH ₂ SR ² (I)
(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 12 carbon atoms having one or two carboxyl groups)
It relates to an ethylenically unsaturated group-containing resin having a group represented by:

  According to the present invention, a base for a photosensitive resin composition which imparts suitable hardness and elasticity, excellent water resistance and chemical resistance, and is excellent in curability and developability, and a photosensitive resin using the same A composition is provided.

  The base for the photosensitive resin composition of the present invention has one major feature in that an ethylenically unsaturated group-containing resin having a group represented by the formula (I) is used. Since the base for a photosensitive resin composition of the present invention uses an ethylenically unsaturated group-containing resin having a group represented by the formula (I), a cured product having suitable hardness and elasticity is formed. And the formed hardened | cured material has the effect that it is excellent also in water resistance and chemical-resistance. Furthermore, since the base for photosensitive resin composition of this invention is excellent also in sclerosis | hardenability and developability, it can be used conveniently for the photosensitive resin composition.

In the ethylenically unsaturated group-containing resin having a group represented by the formula (I), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrocarbon group having 1 to 12 carbon atoms having one or two carboxyl groups. Typical examples of suitable hydrocarbon groups having 1 to 12 carbon atoms used for R ² include alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms. Among these, an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferable, and an alkyl group having 1 to 2 carbon atoms and an aryl group having 6 to 10 carbon atoms are more preferable.

  The weight average molecular weight of the ethylenically unsaturated group-containing resin having a group represented by the formula (I) is 2000 to 100,000, preferably 2500 to 60000, more preferably 3000 to 50000, from the viewpoint of developability and photosensitivity. is there.

  The double bond equivalent of the ethylenically unsaturated group-containing resin having a group represented by the formula (I) is 170 to 600, preferably 180 to 500, more preferably 180 to 600, from the viewpoint of photosensitivity and chemical resistance. 400.

  The acid value of the ethylenically unsaturated group-containing resin having a group represented by the formula (I) is preferably 5 to 150 mgKOH / g, more preferably 10 to 100 mgKOH / g, from the viewpoint of developability and chemical resistance. is there.

Examples of the ethylenically unsaturated group-containing resin having a group represented by the formula (I) include an ethylenically unsaturated group-containing resin and a formula (II):
HSR ² (II)
(Wherein R ² is the same as above)
It can prepare by making the mercapto compound represented by these react.

  The weight average molecular weight of the ethylenically unsaturated group-containing resin is 1000 to 80000, preferably 1500 to 50000, more preferably 2000 to 40000, from the viewpoint of developability and photosensitivity.

  The double bond equivalent of the ethylenically unsaturated group-containing resin is 170 to 600, preferably 180 to 500, more preferably 180 to 400, from the viewpoints of photosensitivity and chemical resistance.

  The ethylenically unsaturated group-containing resin has a functional group for reacting with the mercapto compound represented by the formula (II), for example, a functional group such as an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.

  The ethylenically unsaturated group-containing resin can be prepared, for example, by reacting an epoxy group-containing resin with a compound having an ethylenically unsaturated double bond and a carboxyl group.

  The epoxy group-containing resin may be an epoxy resin that is generally used as a raw material of a photosensitive resin composition such as a phenol novolac resin or a cresol novolac resin, or may be manufactured by the following manufacturing method. .

  Examples of the method for producing an epoxy group-containing resin include a method of polymerizing a monomer composition containing an epoxy group-containing monomer.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-epoxycyclohexyl (meth) acrylate, and allyl glycidyl ether. .

  In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”.

  The monomer composition may be composed only of an epoxy group-containing monomer, or, in addition to the epoxy group-containing monomer, a monomer copolymerizable with the epoxy group-containing monomer if necessary. It may be contained.

  Examples of the monomer copolymerizable with the epoxy group-containing monomer include aliphatic (meth) acrylates having 1 to 4 carbon atoms in the ester portion such as methyl (meth) acrylate and butyl (meth) acrylate, Aromatic (meth) acrylate such as cyclodecyl methacrylate, aromatic (meth) acrylate having 6 to 12 carbon atoms such as phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate Hydroxyl group-containing (meth) acrylates such as, styrene and styrene derivatives, N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide, and the like. These may be used alone or in combination of two or more. Also good.

  From the viewpoint of increasing the photosensitivity of the base for the photosensitive resin composition, the content of the epoxy group-containing monomer in the monomer composition is preferably 30 to 100% by weight, more preferably 50 to 100% by weight. The content of the monomer copolymerizable with the epoxy group-containing monomer is preferably 0 to 70% by weight, more preferably 0 to 50% by weight.

  Suitable epoxy group-containing resins include phenol novolac resin, cresol novolac epoxy resin, glycidyl (meth) acrylate homopolymer, glycidyl (meth) acrylate-methyl (meth) acrylate copolymer, glycidyl (meth) acrylate-cyclohexyl maleimide. Examples thereof include a copolymer, a glycidyl (meth) acrylate-tricyclodecyl (meth) acrylate copolymer, and a dicyclopentanyl novolac epoxy resin.

  Examples of the compound having an ethylenically unsaturated double bond and a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, vinylbenzoic acid and crotonic acid, and unsaturated phenols such as parahydroxystyrene. Of these, (meth) acrylic acid is preferred.

  The ratio of the epoxy group-containing resin and the compound having a compound having an ethylenically unsaturated double bond and a carboxyl group is usually an epoxy group-containing resin from the viewpoint of increasing both reactivity and reducing the amount of residual monomers. It is desirable that the amount of the compound having an ethylenically unsaturated double bond and a carboxyl group is 0.9 to 1.2 mol, preferably 0.95 to 1.1 mol per mol.

Further, as the ethylenically unsaturated group-containing resin, for example, an unsaturated carboxylic acid such as (meth) acrylic acid, vinyl benzoic acid or crotonic acid, or a monomer having a phenolic hydroxyl group such as parahydroxystyrene is polymerized. In the polymer obtained in this manner, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-, in a proportion of 5 to 50 parts by weight per 100 parts by weight of the polymer. Ethylenically unsaturated group-containing resins obtained by addition reaction of epoxy group-containing monomers such as epoxycyclohexyl (meth) acrylate and allyl glycidyl ether, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (Meth) acrylate, 2-hydroxy-3-phenylpropyl (meth) acrylate In a polymer obtained by polymerizing a monomer having a hydroxyl group such as a rate at a ratio of 5 to 100 parts by weight per 100 parts by weight of the polymer, (meth) acryloyloxyethyl (meth) acrylate and the like An ethylenically unsaturated group-containing resin obtained by adding an isocyanate-containing monomer, and a polymer obtained by polymerizing an isocyanate-containing monomer such as (meth) acryloyloxyethyl (meth) acrylate In a ratio of 5 to 80 parts by weight per 100 parts by weight of the polymer, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenylpropyl (meth) acrylate Hydroxyl groups such as 2-hydroxy-3-acryloyloxymethacrylate Ethylenically unsaturated group containing resin obtained by adding an monomer to, the control of the double bond equivalent and the molecular weight at the time of preparing the ethylenically unsaturated group-containing resin is easy, preferably.

In the compound represented by the formula (II) to be reacted with the ethylenically unsaturated group-containing resin, R ² is the same as described above.

  Examples of the compound represented by the formula (II) include mercapto compounds such as mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid and mercaptosuccinic acid. These may be used alone or in admixture of two or more.

  The amount of the mercapto compound represented by the formula (II) increases the developability and chemical resistance of the resulting ethylenically unsaturated group-containing resin having the group represented by the formula (I), and increases the reactivity of both. From the viewpoint of stabilization, it is preferably 0.5 to 50 parts by weight, more preferably 1 to 20 parts by weight per 100 parts by weight of the ethylenically unsaturated group-containing resin.

  The reaction between the ethylenically unsaturated group-containing resin and the mercapto compound represented by the formula (II) may be performed without using a solvent, but if necessary, ethyl acetate, butyl acetate, methoxypropylene glycol acetate, Performed in the presence of organic solvents such as esters such as methyl methoxypropionate and ethyl ethoxypropionate, ketones such as methyl ethyl ketone and cyclohexanone, ethers such as diisopropyl ether and diglyme, and aromatic solvents such as toluene and xylene. Also good.

  In the reaction, for example, phosphorus compounds such as triphenylphosphine, amines such as triethylamine, pyridine, dimethylbenzylamine, and catalysts such as quaternary salts thereof can be used. Usually, the amount of the catalyst is preferably about 0.001 to 0.3 mol per mol of the mercapto compound represented by the formula (II).

  The reaction atmosphere and reaction temperature are not particularly limited, but usually the reaction atmosphere may be air or an inert gas such as nitrogen gas or argon gas. Moreover, it is preferable that reaction temperature is about 40-100 degreeC normally.

  The end point of the reaction can be, for example, when the remaining amount of mercapto groups of the mercapto compound represented by the formula (II) is 0.1 wt% or less by iodometric titration.

  Thus, an ethylenically unsaturated group-containing resin having a group represented by the formula (I) is obtained by reacting the ethylenically unsaturated group-containing resin with the mercapto compound represented by the formula (II).

  Suitable examples of the ethylenically unsaturated group-containing resin having a group represented by the formula (I) include glycidyl (meth) acrylate homopolymer, glycidyl (meth) acrylate-methyl (meth) acrylate copolymer, and glycidyl. (Meth) acrylate-cyclohexylmaleimide copolymer, glycidyl (meth) acrylate-tricyclodecyl (meth) acrylate copolymer, cresol novolac epoxy resin, dicyclopentanyl novolac epoxy resin (meth) acrylic acid adduct Resin to which glycolic acid, mercaptopropionic acid or mercaptosuccinic acid is added, (meth) acryloyloxyethyl isocyanate homopolymer, (meth) acryloyloxyethyl isocyanate-methyl (meth) acrylate copolymer, (meth) acryloyloxy Add thioglycolic acid, mercaptopropionic acid or mercaptosuccinic acid of hydroxyethyl (meth) acrylate adduct of siethyl isocyanate-tricyclodecyl (meth) acrylate copolymer, (meth) acryloyloxyethyl isocyanate-cyclohexyl maleimide copolymer Added resin, (meth) acrylic acid-cyclohexylmaleimide copolymer, (meth) acrylic acid-tricyclodecyl (meth) acrylate copolymer, (meth) acrylic acid-styrene copolymer glycidyl (meth) acrylate addition Examples thereof include resins obtained by adding thioglycolic acid, mercaptopropionic acid or mercaptosuccinic acid to the product.

  The acid value of the ethylenically unsaturated group-containing resin having a group represented by the formula (I) is preferably from 5 to 140 mgKOH / g, more preferably from 10 to 80 mgKOH / g, from the viewpoint of developability and chemical resistance. is there.

  The base for a photosensitive resin composition of the present invention contains an ethylenically unsaturated group-containing resin having a group represented by the formula (I). The base for the photosensitive resin composition of the present invention may be composed only of an ethylenically unsaturated group-containing resin having a group represented by the formula (I), or within the range in which the object of the present invention is not hindered. In addition, other resins may be contained.

  The photosensitive resin composition of the present invention is a base for a photosensitive resin composition containing an ethylenically unsaturated group-containing resin having a group represented by formula (I), a polyfunctional monomer, and a photopolymerization initiator. It contains.

  The content of the base for the photosensitive resin composition in the photosensitive resin composition is preferably 1 to 60% by weight, more preferably 2 to 50% from the viewpoints of photocurability, tackiness, chemical resistance and developability. % By weight.

  Examples of the multifunctional monomer include 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Examples include hexa (meth) acrylate of a caprolactone modified product of erythritol.

  The content of the crosslinkable monomer in the photosensitive resin composition is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, from the viewpoints of photocurability, tackiness, chemical resistance and developability.

  Examples of the photopolymerization initiator include 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, hydroxy-2-methyl-1-phenyl (4-dodecyl) propan-1-one, 2 Acetophenone photopolymerization initiators such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, benzophenones such as benzophenone, 3,3-dimethyl-4-methoxybenzophenone, dimethylaminobenzophenone Photopolymerization initiators, benzoin photopolymerization initiators such as benzyldimethyl ketal and benzoin isopropyl ether, thioxanthone photopolymerization initiators such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, 2- ( Imida such as 2,3-dichlorophenyl) -4,5-bis (3-methoxyphenyl) imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-diphenylimidazole dimer Sol-based photopolymerization initiator, 2,4,6-tris (trichloromethyl) -s-triazine, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and the like, and these can be used alone or in admixture of two or more. Among these, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like are preferable.

  The content of the photopolymerization initiator in the photosensitive resin composition is preferably 1 to 40% by weight, more preferably 2 to 25% by weight, from the viewpoint of photocurability.

  If necessary, an organic solvent can be used in the photosensitive resin composition of the present invention. Examples of the organic solvent include esters such as ethyl acetate, butyl acetate, methoxypropylene glycol acetate, methyl methoxypropionate and ethyl ethoxypropionate, ketones such as methyl ethyl ketone and cyclohexanone, ethers such as diisopropyl ether and diglyme, and toluene. An aromatic organic solvent such as xylene may be used, but the present invention is not limited to such examples.

  The amount of the organic solvent is not particularly limited, but usually from the viewpoint of viscosity and coating properties of the photosensitive resin composition of the present invention, preferably 100 to 800 parts by weight with respect to 100 parts by weight of the photosensitive resin composition. More preferably, it is 150 to 500 parts by weight.

  Moreover, additives, such as a plasticizer, a leveling agent, an antifoamer, a coloring agent, can be added to the photosensitive resin composition of this invention as needed, for example.

  Since the photosensitive resin composition of the present invention is excellent in hardness, elasticity, durability, chemical resistance and developability, it can be suitably used for inks, adhesives, insulating materials, electronic materials, and the like. .

  When the photosensitive resin composition of the present invention is applied to a substrate, examples of the application method include a spray coating method, a roll coating method, and a dipping method, but the present invention is limited only to such examples. It is not something.

  Examples of the substrate to which the photosensitive resin composition of the present invention can be applied include metal substrates such as iron, copper, and stainless steel, glass substrates, epoxy resins, acrylic resins such as polymethyl methacrylate, polycarbonate, Although resin-made base materials, such as polyester, are mentioned, this invention is not limited only to this illustration.

  In addition, the thickness of the coating film after application of the photosensitive resin composition of the present invention varies depending on the application and the like, and thus cannot be unconditionally determined, but is usually preferably about 0.1 to 50 μm.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

Example 1
(1) Preparation of photosensitive resin A In a five-necked reaction vessel with an internal volume of 2 liters, 544 g of propylene glycol monomethyl ether acetate, 284 g of glycidyl methacrylate, 71 g of methyl methacrylate and 17 g of azobisisobutyronitrile were added, and nitrogen gas was added. Then, the mixture was heated at 80 ° C. for 6 hours to obtain a polymer solution of glycidyl methacrylate-methyl methacrylate copolymer.

  Next, 144 g of acrylic acid, 0.04 g of methoquinone and 0.4 g of triphenylphosphine are added to the obtained polymer solution, and heated at 100 ° C. for 24 hours while blowing air, and acrylic acid of glycidyl methacrylate-methyl methacrylate copolymer. A reaction mixture containing the adduct was obtained.

  Next, 45 g of mercaptoacetic acid and 0.5 g of N, N-dimethylbenzylamine were added to the obtained reaction mixture, and the mixture was heated at 50 ° C. for 24 hours, whereby a photosensitive resin A reaction solution (photosensitive resin A solid solution Content: 50% by weight).

5 g of this reaction solution was dropped into 50 g of cyclohexane to precipitate photosensitive resin A, and the precipitated photosensitive resin A was washed with cyclohexane and dried to obtain powdered photosensitive resin A. Infrared absorption (IR) spectrum and nuclear magnetic resonance ( ¹ H-NMR) spectrum of the obtained photosensitive resin A were measured according to the following method. The results are shown in FIGS. 1 and 2, respectively.

[Infrared absorption (IR) spectrum]
Using an infrared absorption (IR) spectrum measuring apparatus [manufactured by Shimadzu Corporation, product number: FTIR-4200], the measurement was performed by a liquid film method (sodium chloride plate).

[Nuclear magnetic resonance ( ¹ H-NMR) spectrum]
Using a nuclear magnetic resonance ( ¹ H-NMR) spectrometer (manufactured by JEOL Ltd., product number: JNM-AL300), measurement was performed at 300 MHz, internal standard TMS, and deuterated chloroform.

Moreover, elemental analysis of the obtained photosensitive resin A was performed. The results are shown below.
[Elemental analysis]
Measurement was performed using a product name: Microcoder JM10 manufactured by J Science Lab.
Calculated values: C54.0 wt%, H6.6 wt%, S2.9 wt%
Actual value: C54.7 wt%, H6.8 wt%, S2.3 wt%

  Next, the acid value, double bond equivalent, and weight average molecular weight of the obtained photosensitive resin A were measured based on the following methods. The results are shown in Table 1.

[Acid value]
Measurement was performed with 0.5 mol / L sodium hydroxide aqueous solution using phenolphthalein as an indicator.

[Double bond equivalent]
The double bond equivalent of the photosensitive resin is given by the formula:
[Double bond equivalent]
= [Resin solid content of photosensitive resin A ÷ (number of moles of monomer added when producing resin having ethylenically unsaturated group−added to resin having ethylenically unsaturated group, formula ( II) Number of moles of mercapto group of the mercapto compound represented by
Based on.

(Weight average molecular weight)
It was measured by gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120, column: G-5000HXL and G-3000HXL, two detectors, detector: RI].

  From the above results, the obtained photosensitive resin A is a random copolymer composed of 74 mol% 3-acryloyl-2-hydroxypropyl methacrylate repeating units and 26 mol% methyl methacrylate repeating units. It is added to the acryloyl group and has a weight average molecular weight of 30000.

(2) Preparation of photosensitive resin composition A The reaction solution of the photosensitive resin A obtained above was left as it was without isolating the photosensitive resin A from the solution. Used as. 200 parts by weight of the reaction solution of the photosensitive resin A, 100 parts by weight of dipentaerythritol hexaacrylate, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [manufactured by Ciba Geigy, trade name: Irgacure 907] A photosensitive resin composition A was obtained by mixing 15 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA).

Example 2
(1) Preparation of photosensitive resin B In a five-necked reaction vessel with an internal volume of 1 liter, 419 g of propylene glycol monomethyl ether acetate, phenol novolac epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name: EPPN-201 ( Epoxy equivalent: 190)] 264 g, 100 g of acrylic acid, 0.07 g of methoquinone and 1.8 g of triphenylphosphine were added and heated at 100 ° C. for 48 hours while blowing air to obtain a reaction mixture of acrylic acid adduct of novolak resin. .

  Next, 55 g of mercaptobenzoic acid was added to the obtained reaction mixture and heated at 70 ° C. for 24 hours to obtain a reaction solution of photosensitive resin B (solid content of photosensitive resin B: 50% by weight).

  The acid value, double bond equivalent and weight average molecular weight of the obtained photosensitive resin B were measured in the same manner as in Example 1. The results are shown in Table 1.

  From the above results, the obtained photosensitive resin B is a condensate of 3-acryloyl-2-hydroxypropyloxybenzene, mercaptobenzoic acid is added to the acryloyl group, and has a weight average molecular weight of 2000. Recognize.

(2) Preparation of photosensitive resin composition B The photosensitive resin composition base obtained without changing the photosensitive resin B reaction solution obtained as described above without isolating the photosensitive resin B from the solution. Used as. 200 parts by weight of a reaction solution of this photosensitive resin B, 100 parts by weight of dipentaerythritol hexaacrylate, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [manufactured by Ciba Geigy, trade name: Irgacure 907] A photosensitive resin composition B was obtained by mixing 15 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA).

Example 3
(1) Preparation of photosensitive resin C In a five-necked reaction vessel having an internal volume of 2 liters, 740 g of propylene glycol monomethyl ether acetate, 310 g of methacryloyloxyethyl isocyanate, 148 g of tricyclodecyl methacrylate and 19 g of azobisisobutyronitrile In addition, the mixture was heated at 80 ° C. for 6 hours while blowing nitrogen gas to obtain a polymer solution of methacryloyloxyethyl isocyanate-tricyclodecyl methacrylate copolymer.

  Next, 232 g of 2-hydroxyethyl acrylate and 0.04 g of methoquinone were added to the obtained polymer solution, heated at 60 ° C. for 24 hours while blowing air, and the methacryloyloxyethyl isocyanate-tricyclodecyl methacrylate copolymer 2- A reaction mixture containing a hydroxyethyl acrylate adduct was obtained.

  To the obtained reaction mixture, 50 g of mercaptosuccinic acid and 0.5 g of N, N-dimethylbenzylamine were added and heated at 50 ° C. for 24 hours to obtain a reaction solution of photosensitive resin C (solid content of photosensitive resin C). Content: 50% by weight).

  The acid value, double bond equivalent and weight average molecular weight of the obtained photosensitive resin C were measured in the same manner as in Example 1. The results are shown in Table 1.

  From the above results, the obtained photosensitive resin C was a random copolymer composed of 75 mol% of 2-acryloyloxyethyl carbamate 2-acryloyloxyethyl repeating units and 25 mol% of tricyclodecyl methacrylate repeating units. It can be seen that mercaptosuccinic acid is added to the acryloyl group and has a weight average molecular weight of 25000.

(2) Preparation of photosensitive resin composition The reaction solution of the photosensitive resin C obtained above was used as a base for the photosensitive resin composition in the state without isolating the photosensitive resin C from the solution. Using. 200 parts by weight of a reaction solution of the photosensitive resin C, 100 parts by weight of dipentaerythritol hexaacrylate, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [manufactured by Ciba Geigy, trade name: Irgacure 907] A photosensitive resin composition C was obtained by mixing 15 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA).

Example 4
(1) Preparation of photosensitive resin D In a five-necked reaction vessel with an internal volume of 2 liters, 567 g of propylene glycol monomethyl ether, 172 g of methacrylic acid, 74 g of cyclohexylmaleimide and 19 g of azobisisobutyronitrile were added, and nitrogen gas was added. While blowing, the mixture was heated at 80 ° C. for 6 hours to obtain a polymer solution of methacrylic acid-cyclohexylmaleimide copolymer.

  Next, 284 g of glycidyl methacrylate and 0.04 g of methoquinone are added to the obtained polymer solution, heated at 60 ° C. for 24 hours while blowing air, and a reaction mixture containing a glycidyl methacrylate adduct of a methacrylic acid-cyclohexylmaleimide copolymer is prepared. Obtained.

  To the obtained reaction mixture, 37 g of mercaptosuccinic acid and 0.5 g of N, N-dimethylbenzylamine were added and heated at 50 ° C. for 24 hours to obtain a reaction solution of photosensitive resin C (solid content of photosensitive resin D). Content: 50% by weight).

  The acid value, double bond equivalent and weight average molecular weight of the obtained photosensitive resin D were measured in the same manner as in Example 1. The results are shown in Table 1.

  From the above results, the obtained photosensitive resin D is a random copolymer composed of 81 mol% of 3-methacryloyl-2-hydroxypropyl methacrylate repeating units and 19 mol% of cyclohexylmaleimide repeating units. Mercaptosuccinic acid Is added to the methacryloyl group and has a weight average molecular weight of 25,000.

(2) Preparation of photosensitive resin composition The reaction solution of photosensitive resin D obtained above was used as the base for the photosensitive resin composition in the state without isolating photosensitive resin D from the solution. Using. 200 parts by weight of a reaction solution of this photosensitive resin D, 100 parts by weight of dipentaerythritol hexaacrylate, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [manufactured by Ciba Geigy, trade name: Irgacure 907] A photosensitive resin composition D was obtained by mixing 15 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA).

Comparative Example 1
(1) Preparation of photosensitive resin E In a five-neck reaction vessel with an internal volume of 2 liters, 689 g of propylene glycol monomethyl ether acetate, 284 g of glycidyl methacrylate, 71 g of methyl methacrylate and 17 g of azobisisobutyronitrile were added, and nitrogen gas was added. Was heated at 80 ° C. for 6 hours while blowing to obtain a reaction solution of polyglycidyl methacrylate.

  Next, 144 g of acrylic acid, 0.04 g of methoquinone, and 0.4 g of triphenylphosphine are added to the obtained reaction solution, and the mixture is heated at 100 ° C. for 24 hours while blowing air to contain an acrylic acid adduct solution of polyglycidyl methacrylate. A reaction mixture was obtained.

  To the obtained reaction mixture, 190 g of tetrahydrophthalic anhydride was added and heated at 70 ° C. for 10 hours to obtain a reaction solution of photosensitive resin E (solid content of photosensitive resin E: 50% by weight). .

  The acid value, double bond equivalent and weight average molecular weight of the obtained photosensitive resin E were measured in the same manner as in Example 1. The results are shown in Table 1.

(2) Preparation of photosensitive resin composition E The photosensitive resin E was used as a base for the photosensitive resin composition as it was without being isolated from the reaction solution of the photosensitive resin E obtained above. 200 parts by weight of a reaction solution of the photosensitive resin E, 100 parts by weight of dipentaerythritol hexaacrylate, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [manufactured by Ciba Geigy, trade name: Irgacure 907] 15 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were mixed to obtain a photosensitive resin composition E.

Comparative Example 2
(1) Preparation of photosensitive resin F In a five-necked reaction vessel with an internal volume of 2 liters, 507 g of propylene glycol monomethyl ether, 172 g of methacrylic acid, 115 g of cyclohexylmaleimide and 17 g of azobisisobutyronitrile were added, and nitrogen gas was added. While blowing, the mixture was heated at 80 ° C. for 6 hours to obtain a reaction solution.

  Next, 220 g of glycidyl methacrylate, 0.04 g of methoquinone and 0.4 g of triphenylphosphine were added to the obtained reaction solution, and the mixture was heated at 100 ° C. for 24 hours while blowing air, and glycidyl methacrylate of a methacrylic acid-cyclohexyl maleimide copolymer. A reaction solution of photosensitive resin F containing an adduct solution was obtained (solid content of photosensitive resin E: 50% by weight).

  The acid value, double bond equivalent and weight average molecular weight of the obtained photosensitive resin F were measured in the same manner as in Example 1. The results are shown in Table 1.

(2) Preparation of photosensitive resin composition E The photosensitive resin E was used as a base for the photosensitive resin composition as it was without being isolated from the reaction solution of the photosensitive resin E obtained above. 200 parts by weight of a reaction solution of the photosensitive resin E, 100 parts by weight of dipentaerythritol hexaacrylate, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one [manufactured by Ciba Geigy, trade name: Irgacure 907] 15 parts by weight and 400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were mixed to obtain a photosensitive resin composition F.

  Next, as the physical properties of the resin compositions obtained in each Example and each Comparative Example, hardness, elastic modulus, water resistance, chemical resistance, curability and developability were evaluated based on the following methods. The results are shown in Table 2.

(1) Hardness The dynamic hardness of the cured film obtained by applying and curing a photosensitive resin plastic to a glass substrate to a thickness of 10 μm is applied to a dynamic micro hardness tester (manufactured by Shimadzu Corporation, triangular pyramid indenter, load 20 mN). Measured.

(2) Modulus of elasticity A cured film made by applying a photosensitive resin plastic material to a glass substrate and curing it to a thickness of 10 μm with a dynamic micro hardness tester (manufactured by Shimadzu Corporation, triangular pyramid indenter, load 20 mN) Measure the plastic deformation amount and total deformation amount, the formula:
[Elastic modulus (%)] = [(total deformation amount−plastic deformation amount) ÷ (total deformation amount)] × 100
Based on this, the elastic modulus was determined.

(3) Water resistance A photosensitive resin plastic material is applied to a glass substrate and cured, and a cured film having a thickness of 10 μm is immersed in boiling water. After 4 hours, the film is taken out from boiling water. According to the regulations, a “cross cut test” was performed. The evaluation criteria are shown below.
(Evaluation criteria)
○: No peeling of the grid pattern △: Partial peeling of the grid pattern ×: Full peeling of the grid pattern

(4) Chemical resistance When a drop of 10% sodium hydroxide aqueous solution is dropped on a cured film that has been coated and cured on a glass substrate to a thickness of 10μm and wiped off after 10 minutes. The state of the coating film was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: No abnormality △: Slightly scratched ×: Swelled coating

(5) Curability A photosensitive resin plastic was applied to a glass substrate and dried under reduced pressure to prepare a sample. Next, the sample was irradiated with ultraviolet rays (light source: 2 kW high-pressure mercury lamp, 80 W / cm, distance from the light source of 30 cm) and irradiated with 100 mJ. After UV irradiation, 1 drop of acetone was dropped on the coating film and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: No abnormality ×: Dissolved in coating film

(6) Developability A photosensitive resin plastic was applied to a glass substrate and dried under reduced pressure to form a 10 μm coating film, which was used as a specimen. The specimen was immersed in a 0.2% aqueous sodium carbonate solution, and the state of the coating film at that time was observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: The coating dissolves in less than 30 seconds △: The coating dissolves in 30 seconds or more but less than 100 seconds ×: There is a residual dissolution when 100 seconds have elapsed

  From the results shown in Tables 1 and 2, the photosensitive resin compositions obtained in the respective examples are excellent in both developability and chemical resistance despite the low acid value. I understand that.

  On the other hand, although the photosensitive resin composition obtained in Comparative Example 1 is excellent in developability, it can be seen that the acid resistance is high and therefore the chemical resistance is inferior. Moreover, although the photosensitive resin composition obtained by the comparative example 2 has the acid value similar to the photosensitive resin composition obtained by each Example, it turns out that it is inferior to developability.

  The base for a photosensitive resin composition of the present invention and the photosensitive resin composition using the same are useful for, for example, inks, adhesives, insulating materials, and electronic materials.

2 is a diagram showing an infrared absorption (IR) spectrum of the photosensitive resin obtained in Example 1. FIG. 1 is a diagram showing a nuclear magnetic resonance ( ¹ H-NMR) spectrum of a photosensitive resin obtained in Example 1. FIG.

Claims (4)

Formula (I):
_{^{-OCOCH (R 1) CH 2 SR}} 2 (I)
(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 12 carbon atoms having one or two carboxyl groups)
The base for photosensitive resin compositions characterized by containing the ethylenically unsaturated group containing resin which has group represented by these. An ethylenically unsaturated group-containing resin having a group represented by the formula (I) is an ethylenically unsaturated group-containing resin and a formula (II):
HSR ² (II)
(Wherein R ² represents a C 1-12 hydrocarbon group having one or two carboxyl groups)
The base for a photosensitive resin composition according to claim 1, which is a reaction product with a mercapto compound represented by the formula: Formula (I):
_{^{-OCOCH (R 1) CH 2 SR}} 2 (I)
(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 12 carbon atoms having one or two carboxyl groups)
A photosensitive resin composition comprising a base for a photosensitive resin composition containing an ethylenically unsaturated group-containing resin having a group represented by formula (I), a polyfunctional monomer, and a photopolymerization initiator. Formula (I):
_{^{-OCOCH (R 1) CH 2 SR}} 2 (I)
(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrocarbon group having 1 to 12 carbon atoms having one or two carboxyl groups)
An ethylenically unsaturated group-containing resin having a group represented by:

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